EP1826285B1 - Acier inoxydable martensitique - Google Patents
Acier inoxydable martensitique Download PDFInfo
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- EP1826285B1 EP1826285B1 EP05799225A EP05799225A EP1826285B1 EP 1826285 B1 EP1826285 B1 EP 1826285B1 EP 05799225 A EP05799225 A EP 05799225A EP 05799225 A EP05799225 A EP 05799225A EP 1826285 B1 EP1826285 B1 EP 1826285B1
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- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims description 43
- 229910000831 Steel Inorganic materials 0.000 claims description 45
- 239000010959 steel Substances 0.000 claims description 45
- 230000014509 gene expression Effects 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005496 tempering Methods 0.000 description 59
- 239000000463 material Substances 0.000 description 27
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 26
- 239000000523 sample Substances 0.000 description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000010949 copper Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 229910000734 martensite Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 239000003129 oil well Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000003518 caustics Substances 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
Classifications
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- 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 specifically to martensitic stainless steel for use in a corrosive environment including corrosive substances such as hydrogen sulfide, carbon dioxide gas, and chloride ions.
- Martensitic stainless steel having a yield stress (0.2% proof stress) in the range from 758 MPa to 860 MPa hereinafter referred to as "110 ksi grade" and martensitic stainless steel having a strength equal to or higher than the 110 ksi grade have been developed.
- Martensitic stainless steel for oil well must have high corrosion resistance such as SCC (Stress Corrosion Cracking) resistance and SSC (Sulfide Stress Cracking) resistance. This is because oil wells and gas wells exist in corrosive environments that include corrosive substances such as hydrogen sulfide, carbon dioxide gas, and cloride ions. More specifically, martensitic stainless steel for use in oil wells must have high strength, high toughness, and high corrosion resistance.
- Martensitic stainless steel having high strength and high corrosion resistance is disclosed by JP 2003-3243 A .
- the disclosed martensitic stainless steel contains at least 1.5% by mass of Mo and allows higher SSC resistance than conventional martensitic stainless steel to be obtained.
- Fig. 1 shows the relation between the yield stress of martensitic stainless steel with a high Mo content (hereinafter referred to as “high Mo martensitic stainless steel) and the tempering temperature.
- the high Mo martensitic stainless steel in Fig. 1 contains, by mass, 0.016% C, 11.8% Cr, 7.2% Ni, and 2.9% Mo, with the balance being Fe and impurities.
- the gradient of the tempering temperature curve C10 in the yield stress range from 758 MPa to 860 MPa is large.
- the tempering temperature must be about in the range from 580°C to 600°C in order to obtain the 110 ksi grade strength for the high Mo martensitic stainless steel. More specifically, the tempering temperature range ⁇ T that allows the 110 ksi grade strength to be obtained is very small.
- the tempering temperature range ⁇ T is small, the productivity is reduced. In general, several hundred tons of such high Mo martensitic stainless steel is successively produced. In this case, the high Mo martensitic stainless steel is made by a plurality of heats (molten steel produced by a single steel making process) and the chemical compositions of the heats are not completely the same and slightly vary among them. If the tempering temperature range ⁇ T is small, the tempering temperature must be changed every time the chemical composition changes in order to obtain the 110 ksi grade strength for the steel. In short, in order to obtain the 110 ksi grade strength, the tempering temperature must be changed for each of the heats. The necessity of changing the tempering temperature setting in this manner lowers the productivity.
- JP-A 5 156 409 relates to a high-strength martensitic steel having excellent sea water resistance.
- the inventor conducted various experiments and examinations and has obtained the following findings.
- the tempering temperature range that allows the yield stress to be from 758 MPa to 860 MPa can be larger than conventional cases.
- F1 ⁇ 600 because the tempering process is carried out at 600°C or less. If the tempering temperature is set to 600°C or more, microscope carbide or intermetallic compounds in the steel become coarse, and this rather reduces the strength and toughness. Since the tempering temperature is 600°C or less, it is only necessary that F1 be 600°C or more.
- Expression (2) is an expression used to make the steel after tempering martensitic. If the contents of C, Mn, and Ni that are austenite forming elements and the contents of Si, Cr, and Mo that are ferrite forming elements satisfy the relation defined by Expression (2), the structure becomes martensitic, and ⁇ ferrite can be prevented from being produced. Therefore, the strength can be prevented from being lowered, and high toughness can be maintained.
- a tempering temperature curve as curve C1 shown in Fig. 2 can be obtained, and the gradient of the tempering temperature curve in the yield stress range from 758 MPa to 860 MPa can be smaller than that in the conventional cases. Therefore, the tempering temperature range ⁇ T1 that allows the yield stress to be in the range from 758 MPa to 860 MPa is larger than the tempering temperature range ⁇ T2 of the conventional tempering temperature curve C2. Therefore, the decrease in the productivity because of temperature setting changes during operation can be prevented.
- the inventor completed the following invention based on the above-described findings.
- Martensitic stainless steel according to the invention contains, by mass, 0.001% to 0.01% C, at most 0.5% Si, 0.1% to 3.0% Mn, at most 0.04% P, at most 0.01% S, 10% to 15% Cr, 4% to 8% Ni, 2.8% to 5.0% Mo, 0.001% to 0.10% Al, at most 0.07% N, 0% to 0.25% Ti, 0% to 0.25% V, 0% to 0.25% Nb, 0% to 0.25% Zr, 0% to 1.0% Cu, 0% to 0.005% Ca, 0% to 0.005% Mg, 0% to 0.005% La, and 0% to 0.005% Ce, with the balance being Fe and impurities, the steel satisfies Expressions (1) and (2) and has a yield stress in the range from 758 MPa to 860 MPa.
- the gradient of the tempering temperature curve can be reduced by setting the C content to 0.01% or less.
- the A C1 transformation point can be higher than the conventional examples if Expression (1) is satisfied. Therefore, the gradient of the tempering temperature curve is reduced, and the tempering temperature range that allows the yield stress to be in the range from 758 MPa to 860 MPa is increased as compared to the conventional examples.
- the strength can be prevented from being less than 690 MPa (110 ksi) as Expression (2) is satisfied, and the high toughness can be maintained. Since the Mo content is high, high corrosion resistance is obtained.
- the martensitic stainless steel according to the invention preferably contains at least one of 0.005% to 0.25% Ti, 0.005% to 0.25% V, 0.005% to 0.25% Nb, and 0.005% to 0.25% Zr.
- the martensitic stainless steel according to the invention preferably contains 0.05% to 1.0% Cu.
- the martensitic stainless steel according to the invention preferably contains at least one of 0.0002% to 0.005% Ca, 0.0002% to 0.005% Mg, 0.0002% to 0.005% La, and 0.0002% to 0.005% Ce.
- Martensitic stainless steel according to an embodiment of the invention has the following composition.
- % related to each element refers to “% by mass.”
- the C content is excessive, the gradient of the tempering temperature curve becomes steep, and steel having a yield stress in the range from 758 MPa to 860 MPa cannot stably be produced.
- the C content should be limited to a small value. If the C content is less than 0.001%, on the other hand, the manufacturing cost increases. Therefore, the C content is in the range from 0.001% to 0.01%, preferably from 0.001% to 0.008%.
- Silicon is effectively applied as a deoxidizing agent.
- Si hardens steel and therefore an excessive Si content degrades the toughness and workability of the steel.
- Silicon is a ferrite forming element and therefore prevents the steel from becoming martensitic. Therefore, the Si content is not more than 0.5%, preferably 0.3% or less.
- Mn contributes to improvement in the hot workability of the steel. Furthermore, Mn is an austenite forming element and contributes to formation of a martensitic structure. However, an excessive Mn content degrades the toughness. Therefore, the Mn content is in the range from 0.1% to 3.0%, preferably from 0.3% to 1.0%.
- Phosphorus is an impurity and causes SSC to be generated, and therefore the P content is limited as much as possible.
- the P content is 0.04% or less.
- Sulfur is an impurity and lowers the hot workability. Therefore, the S content is limited as much as possible.
- the S content is 0.01% or less.
- Chromium contributes to improvement in corrosion resistance in a wet carbon dioxide gas environment.
- Cr is a ferrite forming element and an excessive Cr content makes it difficult to form tempered martensite, which lowers the strength and the toughness. Therefore, the Cr content is in the range from 10% to 15%, preferably from 11% to 14%.
- Nickel is an austenite forming element and necessary for the structure after tempering to become martensitic. If the Ni content is too small, the structure after the tempering contains much ferrite. On the other hand, an excessive Ni content causes the structure after the tempering to have much austenite. Therefore, the Ni content is in the range from 4% to 8%, preferably from 4% to 7%.
- Molybdenum is a critical element that contributes to improvement in SSC resistance and strength.
- the lower limit for the Mo content to allow high SSC resistance to be obtained is 2.8%.
- Molybdenum is a ferrite forming element and excessive addition of the element prevents the structure from becoming martensitic.
- the upper limit for the Mo content is therefore 5.0%.
- the Mo content is preferably in the range from 2.8% to 4.0%.
- Aluminum is effectively applicable as a deoxidizing agent.
- an excessive Al content causes many inclusions to be generated, and the corrosion resistance is lowered. Therefore, the Al content is from 0.001% to 0.10%, preferably from 0.001% to 0.06%.
- Nitrogen forms a nitride and lowers the corrosion resistance. Therefore, the N content is 0.07% or less.
- the balance consists of Fe and impurities.
- the impurities are mixed in the manufacturing process for various reasons.
- the martensitic stainless steel according to the embodiment further contains at least one of Ti, V, Nb, and Zr if required.
- Ti 0% to 0.25%
- V 0% to 0.25%
- Nb 0% to 0.25%
- Zr 0% to 0.25%
- Ti, V, Nb, and Zr are optional elements. These elements fix C and reduce variations in strength. On the other hand, an excessive content of any of these elements prevents the structure after tempering from becoming martensitic. Therefore, the content of each of these elements is set to the range from 0% to 0.25%, preferably from 0.005% to 0.25%, more preferably from 0.005% to 0.20%.
- the martensitic stainless steel according to the embodiment contains Cu if required.
- Copper is an optional element and an austenite forming element as with Ni suitable for making the structure after tempering martensitic.
- an excessive Cu content lowers the hot workability. Therefore, the Cu content is from 0% to 1.0%, preferably from 0.05% to 1.0%.
- the martensitic stainless steel according to the embodiment further contains at least one of Ca, Mg, La, and Ce if required.
- Ca, Mg, La, and Ce are optional elements. These optional elements contribute to improvement in hot workability. On the other hand, excessive contents of these elements cause coarse oxides to be generated, which lowers the corrosion resistance. Therefore, the contents of these elements are all in the range from 0% to 0.005%, preferably from 0.0002% to 0.005%. Among these elements, Ca and La are elements that particularly contribute to improvement in hot workability.
- the molten steel is formed into a continuos casting material by a continuos casting method.
- the continuos casting material is for example a slab, bloom, or billet.
- the molten steel may be made into ingots by an ingot casting method.
- the slab, bloom, or ingot is formed into billets by hot working. At the time, the billets may be formed by hot rolling or by hot forging.
- the billets produced by the continuos casting or hot working are subjected to further hot working and formed into oil country tubular goods.
- Mannesmann process may be performed as the hot working.
- Ugine-Sejournet hot extrusion process may be employed as the hot working, while a forged pipe making method such as Ehrhardt method may be employed.
- the oil country tubular good after the hot working is subjected to quenching process and tempering process.
- the quenching process is carried out according to a well-known method.
- the quenching temperature is for example from 900°C to 950°C, while other temperature ranges may be employed.
- the lower limit for the tempering temperature is preferably 500°C. If the tempering temperature is too high, retained austenite is precipitated, so that the yield stress cannot be in the range from 758 MPa to 860 MPa. Therefore, the upper limit for the tempering temperature is preferably 600°C.
- the martensitic stainless steel according to the embodiment of the invention satisfies the following Expressions (1) and (2): 922.6 - 554.5 ⁇ C - 50.9 ⁇ Mn + 2944.8 ⁇ P + 1.056 ⁇ Cr - 81.1 ⁇ Ni + 95.8 ⁇ Mo - 125.1 ⁇ Ti - 1584.9 ⁇ Al - 3 76.1 ⁇ N ⁇ 600 30 ⁇ C + 0.5 ⁇ Mn + Ni + 0.5 ⁇ Cu - 1.5 ⁇ Si - Cr - Mo + 7.9 ⁇ 0
- Expression (1) the A c1 transformation point is high, and therefore the gradient of the tempering curve in the yield stress range from 758 MPa to 860 MPa can be reduced.
- Expression (2) the structure can become martensitic in an accelerated manner. Therefore, if both Expressions (1) and (2) are satisfied, the tempering temperature range that allows the yield stress to be in the range from 758 MPa to 860 MPa can be larger than those of the conventional examples. Therefore, a decrease in productivity based on changes in the temperature setting during operation can be reduced.
- the martensitic stainless steel is made into a steel pipe, but the steel may be formed into a steel plate.
- Sample materials having chemical compositions given in Table 1 were produced and each examined for the tempering temperature range that allows the yield stress to be in the range from 758 MPa to 860 MPa. The sample materials were also examined for toughness and corrosion resistance.
- Expressions (1) and (2) are represented as F1 and F2, respectively, and F1 and F2 were obtained for each of the sample materials.
- F1 and F2 were obtained for each of the sample materials.
- "0" is entered in the box for "Ti” in F1 and for those without Cu, "0" is entered in the box for "Cu” in F2.
- F1 and F2 were both within the range according to the invention. More specifically, F1 was 600 or more and F2 was zero or more.
- F1 was less than 600.
- the C content exceeded the upper limit according to the invention.
- F1 was less than 600, and as for the sample material 15, F2 was less than zero.
- the molten steel for the sample materials 1 to 16 were cast into continuous casting materials.
- the produced continuous casting materials were subjected to hot forging and hot rolling and made into a plurality of steel plates each having a thickness of 15 mm, a width of 120 mm, and a length of 1000 mm.
- the steel plates after the hot forging and hot rolling were cooled by air to room temperatures. Using the obtained steel plates, the following tests were conducted.
- the obtained plurality of steel plates were quenched. At the time, the quenching temperature was 910°C. Then, the quenched steel plates were subjected to tempering. At the time, the tempering temperature was varied within the temperature range from 450°C to 650°C. The steel plates after the tempering at various temperatures were subjected to tensile tests. More specifically, a round-bar test piece having a diameter of 6.35 mm and a length of 25.4 mm for the parallel part was produced from each of the steel plates. Using the produced round-bar test pieces, tensile tests were conducted at room temperatures based on JIS Z2241 and the yield stresses were obtained. After the tensile tests, the tempering temperature range ⁇ T in which the yield stress was in the range from 758 MPa to 860 MPa was obtained for each of the sample materials. Note that the 0.2% proof stress was set as the yield stress.
- the tempering temperature ranges of the sample materials that allow the yield stress to be in the range from 758 MPa to 860 MPa are given in Table 2.
- ⁇ T represents the difference between the maximum temperature and the minimum temperature among the tempering temperatures at which the yield stresses of the sample materials are from 758 MPa to 860 MPa.
- the unit is "°C.”
- ⁇ T was 40°C or more for each of the sample materials 1 to 11. Meanwhile, ⁇ T was less than 40°C for the sample materials 12 and 13 because F1 was less than 600 for them.
- the sample material 14 had a high C content, F1 was less than 600, and therefore ⁇ T was less than 40°C.
- the sample materials 15 and 16 each had a high C content, and therefore ⁇ T was less than 40°C.
- Fig. 2 shows the relation between the tempering temperature and the yield stress in the sample materials 1 and 14.
- the gradient of the tempering temperature curve C1 of the sample material 1 whose F1 was 600 or more was small in the yield stress range of 758 MPa to 860 MPa and the tempering temperature range ⁇ T1 was 110°C.
- the gradient of the tempering temperature curve C2 was large in the yield stress range from 758 MPa to 860 MPa, and the tempering temperature range ⁇ T2 was as small as 20°C.
- the toughness tests were conducted as follows. The obtained steel plates were quenched at 910°C and tempered so that the yield stresses become values given in Table 3. From each of the tempered steel plates, a V-notch test piece as wide as 10 mm according to JISZ2202 was produced.
- V-notch test pieces were subjected to Charpy impact tests according to JISZ2242 at -40°C and examined for absorbed energy.
- the unit of the absorbed energy in Table 3 is J. Since the F2 values of the sample materials 1 to 11 are all at least zero, the values of the absorbed energy exceeded 100 J, in other words, high toughness resulted. Meanwhile, the F2 value of the sample material 15 was less than zero, and therefore the absorbed energy was low.
- Corrosion resistance in a wet carbon dioxide gas environment was evaluated by conducting carbon dioxide gas corrosion tests.
- a test piece having a width of 20 mm, a thickness of 3 mm, and a length of 50 mm was cut from each of steel plates quenched and tempered in the same conditions as the above toughness evaluation.
- the surface of each test piece was polished with No. 600 emery paper, then degreased, and dried.
- test pieces were immersed for 720 hours in a 25% NaCl aqueous solution in which CO 2 gas at 9.73 atm and H 2 S at 0.014 atm were saturated. Note that the aqueous solution was kept at 165°C during the tests.
- the test pieces were each examined for quantity loss caused by corrosion. More specifically, the corrosion loss was obtained as a value produced by subtracting the weight of a test piece after the test from the weight of the test piece before the test. The presence/absence of local corrosion at the surfaces of the test pieces was visually inspected. It was determined that the piece had high corrosion resistance in a wet carbon dioxide gas environment if the corrosion loss was less than 7.7 g and there was no local corrosion found.
- the sample materials 1 to 11 each had high corrosion resistance.
- the martensitic stainless steel according to the invention is applicable as a steel material for use in a corrosive environment including corrosive substances such as hydrogen sulfide, carbon dioxide gas, and chloride ions.
- the steel is particularly applicable to steel materials for production facilities, geothermal power generation facilities, and carbon dioxide gas removing facilities, and steel pipes used as oil country tubular goods in a wet hydrogen sulfide environment and a wet carbon dioxide gas environment such as oil wells or gas wells.
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- Heat Treatment Of Articles (AREA)
Claims (5)
- Acier inoxydable martensitique, comprenant, en masse, 0,001 % à 0,01 % de C, au plus 0,5 % de Si, 0,1 % à 3,0 % de Mn, au plus 0,04 % de P, au plus 0,01 % de S, 10 à 15 % de Cr, 4 % à 8 % de Ni, 2,8 % à 5,0 % de Mo, 0,001 % à 0,10 % d'Al, au plus 0,07 % de N, 0 % à 0,25 % de Ti, 0 % à 0,25 % de V, 0 % à 0,25 % de Nb, 0 % à 0,25 % de Zr, 0 % à 1,0 % de Cu, 0 % à 0,005 % de Ca, 0 % à 0,005 % de Mg, 0 % à 0,005 % de La et 0 % à 0,005 % de Ce, le complément étant constitué de Fe et d'impuretés, ledit acier satisfaisant les expressions (1) et (2) et ayant une contrainte de limite élastique dans l'intervalle de 758 MPa à 860 MPa.
dans lesquelles les caractères représentant les éléments sont remplacés par les teneurs des éléments en pourcentage en masse. - Acier inoxydable martensitique selon la revendication 1, comprenant au moins un élément parmi 0,005 % à 0,25 % de Ti, 0,005 % à 0,25 % de V, 0,005 % à 0,25 % de Nb et 0,005 % à 0,25 % de Zr.
- Acier inoxydable martensitique selon la revendication 1, comprenant 0,05 % à 1,0 % de Cu.
- Acier inoxydable martensitique selon la revendication 2, comprenant 0,05 % à 1,0 % de Cu ;
- Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 4, comprenant au moins un élément parmi 0,0002 % à 0,005 % de Ca, 0,0002 % à 0,005 % de Mg, 0,0002 % à 0,005 % de La et 0,0002 % à 0,005 % de Ce.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004335241A JP4337712B2 (ja) | 2004-11-19 | 2004-11-19 | マルテンサイト系ステンレス鋼 |
PCT/JP2005/019685 WO2006054430A1 (fr) | 2004-11-19 | 2005-10-26 | Acier inoxydable martensitique |
Publications (3)
Publication Number | Publication Date |
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EP1826285A1 EP1826285A1 (fr) | 2007-08-29 |
EP1826285A4 EP1826285A4 (fr) | 2009-04-08 |
EP1826285B1 true EP1826285B1 (fr) | 2012-10-03 |
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EP05799225A Active EP1826285B1 (fr) | 2004-11-19 | 2005-10-26 | Acier inoxydable martensitique |
Country Status (5)
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US (1) | US20080213120A1 (fr) |
EP (1) | EP1826285B1 (fr) |
JP (1) | JP4337712B2 (fr) |
CN (1) | CN100549204C (fr) |
WO (1) | WO2006054430A1 (fr) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008023702A1 (fr) * | 2006-08-22 | 2008-02-28 | Sumitomo Metal Industries, Ltd. | Acier inoxydable martensitique |
JP5045178B2 (ja) * | 2007-03-26 | 2012-10-10 | 住友金属工業株式会社 | ラインパイプ用ベンド管の製造方法およびラインパイプ用ベンド管 |
CN101956146A (zh) * | 2010-10-12 | 2011-01-26 | 西安建筑科技大学 | 一种油气管线用高强韧超级马氏体不锈钢及其制备方法 |
BR102014005015A8 (pt) | 2014-02-28 | 2017-12-26 | Villares Metals S/A | aço inoxidável martensítico-ferrítico, produto manufaturado, processo para a produção de peças ou barras forjadas ou laminadas de aço inoxidável martensítico-ferrítico e processo para a produção de tudo sem costura de aço inoxidável martensítico-ferrítico |
US10047417B2 (en) * | 2015-03-11 | 2018-08-14 | Aktiebolaget Skf | Continuous caster roll for a continuous casting machine |
US10443114B2 (en) * | 2016-03-04 | 2019-10-15 | Nippon Steel Corporation | Steel material and oil-well steel pipe |
BR112018072904B1 (pt) * | 2016-05-20 | 2022-09-06 | Nippon Steel Corporation | Barra de aço para membro de fundo de poço e membro de fundo de poço |
MX2019002291A (es) * | 2016-09-01 | 2019-07-04 | Nippon Steel & Sumitomo Metal Corp | Material de acero y tuberia de acero para pozos de petroleo. |
EP3533892B1 (fr) * | 2016-10-25 | 2022-11-02 | JFE Steel Corporation | Seamless pipe of martensitic stainless steel for oil well pipe, and method for producing seamless pipe |
AR116495A1 (es) * | 2018-09-27 | 2021-05-12 | Nippon Steel Corp | Material de acero inoxidable martensítico |
US20220033942A1 (en) * | 2018-09-28 | 2022-02-03 | Corning Incorporated | Alloyed metals with an increased austenite transformation temperature and articles including the same |
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 |
JP2023046414A (ja) * | 2020-01-22 | 2023-04-05 | 日鉄ステンレス株式会社 | マルテンサイト系ステンレス鋼板およびマルテンサイト系ステンレス鋼部材 |
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JPH05156409A (ja) * | 1991-11-29 | 1993-06-22 | Nippon Steel Corp | 耐海水性に優れた高強度マルテンサイトステンレス鋼とその製造方法 |
DK0864663T3 (da) * | 1995-09-27 | 2003-09-15 | Sumitomo Metal Ind | Svejsede stålstrukturer med høj styrke og fremragende korrosionsmodstand |
US6186658B1 (en) * | 1997-03-14 | 2001-02-13 | Nippon Mitsubishi Oil Corporation | Apparatus for mixing a fluid feedstock with particles |
JP3555579B2 (ja) * | 1997-07-18 | 2004-08-18 | 住友金属工業株式会社 | 高耐食性マルテンサイト系ステンレス鋼 |
JP2000192196A (ja) * | 1998-12-22 | 2000-07-11 | Sumitomo Metal Ind Ltd | 油井用マルテンサイト系ステンレス鋼 |
JP2001107198A (ja) * | 1999-10-07 | 2001-04-17 | Nippon Steel Corp | 耐ssc性に優れたマルテンサイト系ステンレス鋼ラインパイプおよびその製造方法 |
US6793744B1 (en) * | 2000-11-15 | 2004-09-21 | Research Institute Of Industrial Science & Technology | Martenstic stainless steel having high mechanical strength and corrosion |
JP2003129190A (ja) * | 2001-10-19 | 2003-05-08 | Sumitomo Metal Ind Ltd | マルテンサイト系ステンレス鋼およびその製造方法 |
AR042494A1 (es) * | 2002-12-20 | 2005-06-22 | Sumitomo Chemical Co | Acero inoxidable martensitico de alta resistencia con excelentes propiedades de resistencia a la corrosion por dioxido de carbono y resistencia a la corrosion por fisuras por tensiones de sulfuro |
AU2004258030B2 (en) * | 2003-07-22 | 2008-08-28 | Nippon Steel Corporation | Martensitic stainless steel |
-
2004
- 2004-11-19 JP JP2004335241A patent/JP4337712B2/ja active Active
-
2005
- 2005-10-26 CN CNB2005800396559A patent/CN100549204C/zh not_active Expired - Fee Related
- 2005-10-26 EP EP05799225A patent/EP1826285B1/fr active Active
- 2005-10-26 US US11/791,015 patent/US20080213120A1/en not_active Abandoned
- 2005-10-26 WO PCT/JP2005/019685 patent/WO2006054430A1/fr active Application Filing
Also Published As
Publication number | Publication date |
---|---|
US20080213120A1 (en) | 2008-09-04 |
EP1826285A1 (fr) | 2007-08-29 |
WO2006054430A1 (fr) | 2006-05-26 |
CN101061245A (zh) | 2007-10-24 |
CN100549204C (zh) | 2009-10-14 |
JP4337712B2 (ja) | 2009-09-30 |
EP1826285A4 (fr) | 2009-04-08 |
JP2006144069A (ja) | 2006-06-08 |
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