WO2005073422A1 - オーステナイト・フェライト系ステンレス鋼 - Google Patents
オーステナイト・フェライト系ステンレス鋼 Download PDFInfo
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- WO2005073422A1 WO2005073422A1 PCT/JP2005/001555 JP2005001555W WO2005073422A1 WO 2005073422 A1 WO2005073422 A1 WO 2005073422A1 JP 2005001555 W JP2005001555 W JP 2005001555W WO 2005073422 A1 WO2005073422 A1 WO 2005073422A1
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- mass
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- stainless steel
- austenitic
- austenite phase
- Prior art date
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 121
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 213
- 230000007797 corrosion Effects 0.000 claims abstract description 136
- 238000005260 corrosion Methods 0.000 claims abstract description 136
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 239000010935 stainless steel Substances 0.000 claims abstract description 39
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 39
- 229910000831 Steel Inorganic materials 0.000 claims description 169
- 239000010959 steel Substances 0.000 claims description 169
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 45
- 229910052804 chromium Inorganic materials 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 23
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000009864 tensile test Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920001074 Tenite Polymers 0.000 claims description 2
- 238000000137 annealing Methods 0.000 description 51
- 230000000694 effects Effects 0.000 description 38
- 239000011651 chromium Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 26
- 229910000734 martensite Inorganic materials 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 238000005097 cold rolling Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 13
- 239000010953 base metal Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
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- 230000002829 reductive effect Effects 0.000 description 11
- 238000003466 welding Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 206010070834 Sensitisation Diseases 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- 230000000670 limiting effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 230000036961 partial effect Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 238000004453 electron probe microanalysis Methods 0.000 description 5
- 238000005098 hot rolling Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 229910003470 tongbaite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 210000000689 upper leg Anatomy 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XLVAVZLFABUPKX-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Cu+4].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Cu+4].S(=O)(=O)([O-])[O-] XLVAVZLFABUPKX-UHFFFAOYSA-J 0.000 description 1
- DBNJSZYFWVVQBO-UHFFFAOYSA-N SOOS Chemical compound SOOS DBNJSZYFWVVQBO-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
- C22C38/18—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
Definitions
- the present invention relates to a stainless steel with austenite and ferrite (two-phase) structure containing low Ni and high N. '' '' Background technology
- Stainless steel is used as a material having excellent corrosion resistance in a wide range of fields, such as automotive components, architectural components, and kitchen appliances. For wheel caps for automobiles, materials that combine high punch setchability and crevice corrosion resistance are required. Stainless steels are commonly found in steels. It is classified into four. Of these, SUS 304 and SUS301 (JIS (Japanese Industrial
- Austenitic stainless steels represented by Standard are most commonly used because of their excellent corrosion resistance and workability. Of these, austenitic stainless steel sheets are most commonly used as stainless steel sheets for automobile wheel caps.
- austenitic stainless steel has higher workability than other stainless steels, it has a problem that it is expensive because it contains a large amount of expensive Ni.
- austenitic stainless steels are susceptible to seasoned cracks when processed to near the forming limit, and have high sensitivity to stress corrosion cracking (SCC). like,
- austenitic stainless steel represented by SUS301 has problems such as corrosion in the bay area due to flying salt, and in snowfall area due to snow melting salt, particularly in the gap (gap) between the wheel and the cap. It has been pointed out that corrosion resistance is inadequate, as seen occasionally.
- it is expensive because it generally contains more than 6% Ni
- Ferritic stainless steel on the other hand, can be improved in corrosion resistance and crevice corrosion resistance by increasing the Cr content, and has excellent properties that it is unlikely to cause cracks or stress corrosion cracking. Having.
- ferritic stainless steel has a drawback that it is inferior in workability, particularly in strength-ductility balance, to austenitic stainless steel.
- the overhangability is much lower than that of austenitic stainless steel, and it is difficult to form.
- martensitic stainless steel has insufficient stretch formability and crevice corrosion resistance.
- Japanese Patent Application Laid-Open No. 08-020843 discloses that a ferritic stainless steel sheet containing 5 to 60% by weight of Cr reduces the contents of C and N and adds appropriate amounts of Ti and b. Disclosed are a steel sheet having excellent deep drawability and a method for producing the same. However, in order to improve the deep drawability, the steel sheet disclosed in Japanese Patent Application Laid-Open No. 08-020843 has a C and N content of 0.03 wt ° / C respectively.
- austenitic / ferritic stainless steel which is located between the austenitic and ferritic stainless steels, has recently attracted attention.
- This austenitic / ferritic stainless steel has excellent corrosion resistance.
- Ferritic austenitic stainless steel has excellent strength and corrosion resistance, and is used as a corrosion-resistant material for highly corrosive environments such as seawater and severe corrosive environments such as oil wells. Therefore, SUS 329-based ferritic austenitic stainless steel specified in JIS contains expensive 4% or more of Ni (mass ratio, same hereafter), so it is expensive and large amount of valuable Ni resources. There is a problem of consumption.
- Japanese Patent Application Laid-Open No. 11-11643 discloses that the amount of Ni added is limited to more than 0.1% and less than 1%, and the austenite stability index (IM index : 551-805 (C + N)%-8.52Si./. 8.57Mn%-12.51Cr%-36.02Ni%-34.52Cu%-13.96Mo%) within the range of 40 to 115
- IM index 551-805 (C + N)%-8.52Si./. 8.57Mn%-12.51Cr%-36.02Ni%-34.52Cu%-13.96Mo%
- the austenitic and ferritic stainless steel sheet disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 11-0 71643 is still insufficient even though the ductility is improved.
- the deep drawability was not sufficient. Therefore, there is a problem that it is still difficult to apply to an application in which extreme overhang forming and hydraulic forming are performed, and it is also difficult to apply to an application in which extreme deep drawing is performed.
- the ferrite 'austenitic stainless steel copper disclosed in Japanese Patent Application Laid-Open No. 11-0 71643 has a high tensile elongation, it has a high gap resistance because it contains a large amount of Mn.
- Mn a problem that the corrosiveness of the part is insufficient and the overhang formability is unknown.
- the corrosion resistance of the weld is inferior.
- ferritic and austenitic stainless steels are used after being welded according to the application, so they must have excellent weld corrosion resistance. Therefore, N, which is an austenite forming element, is added in the range of 0.:! To 0.3% in order to reduce M. The dissolved N precipitates as chromium nitride, causing a problem that the corrosion resistance is degraded due to the formation of a depleted region.
- N is added as an austenite-forming element in the range of 0.1 to 0.34. Therefore, when the cooling rate after solution annealing is low, N precipitates as chromium nitride and the corrosion resistance is deteriorated, so-called sensitization (chromium carbide at grain boundaries, chromium carbide). corrosion deterioration due to the formation of nitrides, since, there has been a problem force S of abbreviated as sensitization) Q
- finish annealed sheets of less than 1.5 thighs are manufactured by steelmaking, steelmaking, hot rolling, hot rolled sheet annealing, descaling by pickling, cold rolling, and finish annealing. Since the material becomes more sensitive during air cooling after the annealing of the strip (plate thickness during annealing: 1.5 to 7), the grain boundaries are preferentially eroded during the subsequent pickling, and these preferential erosion grooves are also obtained during cold rolling. This is a problem that the surface properties of the final finish annealed sheet are remarkably deteriorated because of the disappearance of. To improve surface properties, after hot-rolled sheet annealing Although it is effective to cut the surface with a grinder, it is extremely costly.
- the amount of Mn is lOmass to reduce M. N content 0.35, 0.45 mass. /. Since a large amount of Mn and N are added at the same time, the hot workability is not sufficient, and cracks and flaws are likely to occur during hot working. Although the alloy's cost is low, it includes many cost-increasing factors, such as surface cutting and steel cut-off.
- An object of the present invention is to provide an austenitic ferritic stainless steel having excellent ductility and deep drawability and high formability.
- Another object of the present invention is to provide a ferritic / austenitic stainless steel that solves the above-mentioned problems of the prior art and reduces the amount of Ni while having high overhang formability and corrosion resistance in crevice. Things.
- the present invention solves the above-described problems of the above-mentioned conventional technology, and provides a ferritic / austenitic stainless steel which has relatively low cost, saves Ni resources, and has excellent weld corrosion resistance.
- the purpose is to do.
- Another object of the present invention is to solve the above problems, and an object of the present invention is to provide an austenitic / ferritic stainless steel sheet having excellent intergranular corrosion resistance. Disclosure of the invention
- the inventors evaluated the formability of stainless steel having various components and a steel structure in order to improve the formability of non-austenitic stainless steel containing expensive Ni.
- austenitic / ferritic stainless steel sometimes shows particularly high ductility.
- the cause of this was further investigated.
- the fraction of the austenite phase and the C and N contents in the austenite phase greatly affected the ductility, and in particular, the C, N, and Si in the austenite phase. It has been found that higher ductility can be obtained by adjusting the austenite phase strain stability, which is defined by the contents of, Mn, Cr, Ni, Cu, and Mo, to an appropriate range.
- the austenitic / ferritic stainless steel exhibiting high ductility was also excellent in deep drawability, and thus developed the present invention.
- the inventors have conducted intensive research on a type A austenitic ferritic stainless steel in which the amount of Ni in steel is less than lm ass % and the amount of N in steel is more than 0.05 mass%. Was performed.
- austenite 'ferritic stainless steel with a Mn content of 2niass% or less in steel has improved overhang formability and crevice corrosion resistance.
- the inventors have found that the intergranular corrosion resistance is improved, leading to the present invention.
- the austenitic / ferritic stainless steel of the present invention comprises the following.
- Consisting of a metal structure including a ferrite phase and an austenitic phase the total amount of C and N in the austenitic phase is 0.16 to 2 mass%, and the volume fraction of the austenitic phase is 10 to 85% Austenitic ferritic stainless steel.
- the total elongation in the tensile test is 48% or more.
- C 0.2 mass% or less
- Si 0.2 mass% or less
- Mn 12 mass% or less
- P 0.1 lmass.
- S 0.03 mass% or less
- Cr 15 to 35 mass%
- Ni 3 mass% or less
- N 0.05 to 0.6 mass%
- the balance consisting of Fe and inevitable impurities It is.
- the stainless steel Mn:. 10 mass% or less, Ni: 1 to 3 containing mas S%, the remainder being austenite-ferrite stainless steels consisting of Fe and unavoidable impurities.
- the stainless steel contains Si: 1.2 mass% or less, Mn: 2 mass% or less, M: 1 mass% or less, and ferritic / austenite composed of balance Fe and unavoidable impurities. Stainless steel.
- the stainless steel Si: 1. 2 mass% or less, Mn: 4 ⁇ 1 2 mass% , Ni: 1 containing mas S% or less, the balance being Fe and unavoidable impurities ferrite , Austenitic stainless copper.
- the stainless steel contains Si: 0.4 mass% or less, Mn: 2 to 4 mass%, Ni: 1 mAS s% or less, and the balance is ferrite composed of Fe and unavoidable impurities. ⁇ Austenitic stainless steel.
- C 0.2 mass% or less, Si: 1.2 mass% or less, Mn: 2 mass% or less, P: 0.1 mass% or less, S: 0.03 mass% or less, Cr: 15 mass% 35 mass% or less or more, Ni: 1 mass% or less, N: 0. 05 ma S s % or more 0. 6 mass%% or less, and a balance of Fe and unavoidable non pure product, the austenite phase fraction of metal structure Is 10 or more and 85vol ° / o or less Ferrite's austenitic stainless steel with excellent stretch formability and crevice corrosion resistance.
- C 0.2 mass% or less, Si: 0.4 mass% or less, Mn: 2-4 mass%, P: 0.1 mass% or less, S: 0.03 mass% or less, Cr: 15 mass% or more and 35 mass% or less , M: 1 mass% or less, N: 0.05 mass% or more and 0.6 mass% or less, with the balance being Fe and unavoidable impurities and having an austenite phase fraction of 10 vol% or more and 85 vol% or less.
- Ferritic and austenitic stainless steel with excellent corrosion properties.
- the stainless steel is a ferrite containing, in addition to the above component composition, one or more of Mo: 4 mass% or less and Cu: 4 mass% or less. Austenitic stainless steel.
- the stainless steel is an austenitic / ferritic stainless steel which contains V in an amount of 0.5 mass% or less in addition to the above composition.
- the stainless steel is an austenitic / ferritic stainless steel containing not more than 0.1 lmass% of A1 in addition to the above composition.
- the stainless steel further contains, in addition to the above component composition, B: 0.01 mass% or less, Ca: 0.01 mass% or less, Mg: 0.01 mass% or less, REM:
- Austenitic ferritic stainless steel containing one or more of 0.1% or less of lniass% and Ti: 0.1% or less.
- an austenitic / ferritic stainless steel having high formability excellent in ductility and deep drawability without containing a large amount of expensive Ni can be provided at low cost. Since the austenitic ferritic stainless steel of the present invention has excellent formability, it can be used in the fields of automotive parts ⁇ construction parts, kitchen equipment, etc., and can be subjected to severe stretch forming, deep drawing, and hydroforming such as hydroforming. It is suitable for use in receiving applications.
- the ferrite-austenite stainless steel of the present invention is excellent in overhang property and crevice corrosion resistance despite being relatively inexpensive because of a low Ni content of V. This makes it possible to economically manufacture workpieces of complex shapes such as automobile wheel caps without the risk of placing cracks.
- an austenitic / ferritic stainless steel sheet excellent in corrosion resistance without deterioration of corrosion resistance due to sensitization can be obtained, while having a low Ni content and a high N content.
- the stainless steel sheet of the present invention has a low Ni content, which is preferable from the viewpoint of environmental protection and economical reasons, and also has the above-mentioned excellent characteristics, and can be said to be an industrially useful invention.
- Fig. 1 is a graph showing the effect of the total amount of C and N in the austenite phase and the austenite phase fraction on the total elongation of the austenitic ferritic stainless steel of the present invention.
- FIG. 2 is a graph showing the relationship between the total elongation of the austenitic ferritic stainless steel of the present invention and the work-induced martensite index ⁇ ( ⁇ ) of the austenitic phase.
- Fig. 3 is a graph showing the relationship between the total elongation and the limited drawing ratio (LDR) in the austenitic ferritic stainless steel of the present invention.
- Fig. 4 A graph showing the relationship between the Ni content in the steel sheet, the austenite phase fraction, the total amount of C and N in the austenite phase, and the limiting drawing ratio.
- Figure 5 Graph showing the effect of the Mn content on the stretch formability of ferritic and austenitic stainless steel sheets with a Ni content of 1% or less and an austenite phase fraction of 40-50 vol%.
- Figure 6 Graph showing the effect of the Mn content on the results of an outdoor exposure test of a ferritic austenitic stainless steel sheet with a Ni content of 1% or less and an austenite phase fraction of 40 to 50 vol%.
- Figure 7 Graph showing the relationship between the austenite fraction and the stretch formability (Erichsen value) of ferrite-austenitic stainless steel sheets with Mn content of 2% or less and Ni content of 1% or less.
- Fig. 8 Conceptual diagram showing the crevice resistance corrosion test piece.
- Fig. 9 When the welding test material including the weld zone, the heat-affected zone and the base metal zone is held at a potential of 100 to 300 mV V s SCE for 30 minutes in a 0.035% (mass ratio) sodium chloride solution. 4 is a graph showing the relationship between the presence or absence of corrosion and the Mn content.
- Figure 10 Graph showing the effect of the austenite phase fraction on the corrosion resistance of the weld test material including the base metal.
- the stainless steel of the present invention is an austenitic-ferritic stainless steel mainly composed of an austenite phase and a ferrite phase.
- the volume fraction of the austenitic phase and the contents of C and N contained in the austenitic phase are improved in the formability. It was found that they had a significant effect, and their optimal values were specified. JP2005 / 001555 There is a sign.
- the steel structure other than the austenite phase and the ferrite phase is mainly a martensite phase.
- the fraction of the austenitic phase needs to be 10 to 85% by volume based on the entire structure of the steel. If the austenite phase fraction is less than 10%, high formability cannot be obtained because the austenite phase with excellent ductility is small. On the other hand, if it exceeds 85%, SCC cracks will be scattered.
- the preferred fraction of the austenitic phase is in the range from 15 to 80% by volume.
- the austenite phase fraction is the volume fraction of austenite in the tissue, typically by observing the steel structure under a microscope and determining the ratio of austenite in the tissue by the line method or the area method. Can be determined by measuring Specifically, after polishing the sample, red blood salt solution (potassium ferricyanide (K 3 [Fe (CN) 6 ]): 30 g + potassium hydroxide (KOH): 30 g + water (H 20 ) : 60 ml), the ferrite phase is gray and the austenitic and martensitic phases are white under an optical microscope. The percentage occupied by the gray and white parts is determined by image analysis, and the white part is determined by image analysis. Is defined as the austenite phase fraction.
- the austenite phase and the martensite phase cannot be distinguished, so that not only the austenite phase but also the martensite phase may be contained in the white portion, but, for example, the martensite phase may be contained in the white portion. Even if a phase is included, the effect of the object of the present invention can be obtained if the austenite phase fraction measured by this method and other conditions are satisfied.
- the volume fraction of the austenite phase depends on the steel composition and the annealing conditions in the final annealing process.
- the austenite phase fraction can be controlled by adjusting (temperature, time). Specifically, the lower the Cr, Si, and Mo contents and the higher the C, N, Ni, and Cu contents, the higher the austenite phase fraction. On the other hand, if the annealing temperature is too high, the austenite phase fraction decreases. On the other hand, if the annealing temperature is too low, C and N precipitate as carbonitrides and the amount of solid solution decreases, stabilizing the austenite phase. Contributes to the reduction of the austenite phase fraction. In other words, there is a temperature range where the maximum austenite fraction can be obtained depending on the steel component composition. For light component compositions, the temperature is in the range of 700 to 1300 ° C. The longer the annealing time, the closer the austenite phase fraction in the equilibrium state determined by the steel composition and temperature is. However, it is sufficient to secure about 30 seconds or more.
- the austenitic ferritic stainless steel of the present invention requires that the total amount of C and N contained in the austenitic phase is 0.16 to 2 mass%. If the total amount of C and N in the austenitic phase is less than 0.16 mass%, sufficient formability cannot be obtained because the strength of the work-induced martensite phase is low. On the other hand, if the total amount of C and N content exceeding 2 mas S%, carbides during the cooling after annealing, nitrides large amount deposited, because exerts rather adverse effect on ductility. Preferably, the total amount of C and N ranges from 0.2 to 2 mass%.
- the C and N contents in the austenite phase can be controlled by adjusting the composition of the steel and the annealing conditions (temperature and time).
- the relationship between the composition of the above steel and the annealing conditions is affected by a number of steel components such as C, Si, Mn, Cr, Ni, Cu, and Mo.
- the amount of Cr and Cr is large, the amounts of C and N in the austenite phase often increase.
- C and N are often concentrated in the austenite phase as the austenite phase fraction after annealing for solution treatment becomes lower.
- the measurement of C and N in the austenite phase can be performed by, for example, EPMA.
- the stainless steel of the present invention in which the total amount of C and N in the austenite phase is high, Even when the austenite phase fraction is 5%, the total amount of C and N in the austenite phase is small.
- the hardness of the martensite phase generated in the necking part is higher than that of other stainless steels, and the ductility due to the work-induced martensite phase We believe that the improvement effect has been effectively exhibited.
- C and N in the austenite phase have a remarkable change in the degree of enrichment in the austenite phase depending on the contents of the steel and the heat treatment conditions. Further, the austenite phase is related to the formability, and the higher the austenite phase fraction, the better the formability.
- the austenite phase is stabilized, and .Excellent workability can be obtained by moderately causing process-induced transformation.
- the austenite phase fraction must be 10% or more, and the C + N content in the austenite phase must be 0.16 mass% or more.
- the austenite phase becomes unstable, and most of the austenite phase is transformed into a martensite phase during processing and ductility is reduced. No matter how high the rate, press formability does not improve.
- the reason for limiting the austenite phase fraction to 85% or less is that if it exceeds 85%, SCC susceptibility increases, which is not preferable.
- the stainless steel sheet of the present invention is particularly required to be an austenitic / ferritic stainless steel sheet mainly containing an austenitic phase and a ferrite phase containing 3 mass% or less of Ni. That is, in the present invention, in mainly austenitic / ferritic stainless steel sheets containing 3 mass% or less of Ni, the phase fraction of the austenitic phase and the total amount of C and N contained in the austenitic phase are determined by the press formability. (press formability) has a significant effect.
- the inventors defined the austenitic-ferritic stainless steel of the present invention by the following equation (1) based on the contents of C, N, Si, Mn, Cr, Ni, Cu, and Mo in the austenitic phase.
- the work-induced martensite index (Md ( Y )) of the austenite phase within the range of 30 to 90, even higher ductility can be obtained. It has been found that a total elongation of at least 48% can be obtained. 5 notes
- C (y), ⁇ ( ⁇ ), Si (y), ⁇ ( ⁇ ), Cr (y), ⁇ ( ⁇ ), ⁇ ( ⁇ ), and ⁇ ( ⁇ ) are C in the austenite phase, respectively.
- Md ( Y ) is an index indicating the ease of work-induced martensitic transformation when the austenite phase is processed. This means that martensite transformation is likely to occur.
- the Md (T /) gar 3 Reasons range of 0-90 is preferred, when in the case of less than a 30, the deformation-induced martensitic transformation occurs difficulty fried, fine necking begins to occur, fine necking
- the Md (y) exceeds 90, the austenite phase is transformed into martensite-site transformation in the entire steel before minute necking starts to occur. Therefore, when micro necking starts to occur, the austenite phase, which is the source of work-induced martensite, decreases. Therefore, only when ⁇ (1 ( ⁇ ) is controlled in the range of 1 to 30 to 90, when the micro necking starts to occur, the amount of martensite generated at the necking site is optimized and very high ductility It is considered to indicate.
- the austenitic / ferritic stainless steel of the present invention not only has excellent ductility as described above, but also has high deep drawability.
- the reason for this is that, in deep drawing, especially at corners where deformation tends to concentrate and cracks are likely to occur, the above-mentioned austenitic phase fraction and the total amount of C and ⁇ in the austenitic phase improve ductility.
- the reason for limiting the component composition of the austenitic / ferritic stainless steel sheet according to the present invention will be described. 2005/001555
- C is an important element that increases the austenite phase fraction and is concentrated in the austenite phase to increase the stability of the austenite phase. 0.003 mass to get the effect. /.
- the above is preferable.
- the amount of C is limited to 0.2 mass% or less. Preferably it is less than 0.15 mass%.
- C is less than 0.10 mass%. Preferably, it is limited to 0.05 mass% or less.
- the corrosion resistance of the welded part is excellent in any places of the weld bead, heat-affected zone and base metal. This can be confirmed from Example 4 to be described later.
- the C content in the present invention is set to 0.2 mass% or less, and when considering corrosion cracking resistance, it is set to less than 0.10 mass%, preferably 0.05 mass% or less. This can be confirmed from Tables 10 and 11 of Example 5 described later.
- Si is an element added as a deoxidizing agent. To get that effect
- the content is set to 4 ma SS % or less.
- the content is preferably L 2nia S s% or less.
- Mn is useful as a deoxidizing agent and as an element for adjusting Md (y) in the austenite phase, and can be added as appropriate. 0. Olmass to get the effect. /. The above is preferred. However, if the addition amount exceeds 12 mass%, the hot workability deteriorates. Therefore, the addition amount is preferably 12 mass% or less. Preferably, 10 mass% or less, more preferably 8 mas S% or less. More preferably, it is 7 mass % or less.
- P is an element harmful to hot workability Ya crevice
- the inter corrosion resistance particularly, preferably a so adversely exceeds 0. lmass% becomes remarkable 0. lm ass% or less. More preferably, it is less than 0.05 mass%.
- 03mas S% is a harmful element in the hot workability, in particular, adversely exceeds 0.
- 03mas S% is preferably set to 0. 0 3 mas S% or less so conspicuous. More preferably, it is 0.02 mass% or less.
- Cr is the most important element that imparts corrosion resistance to stainless steel, and if it is less than 15 mass%, sufficient corrosion resistance and crevice corrosion resistance cannot be obtained.
- Cr is a ferrite stabilizing element, and if its amount exceeds 35 mass%, it becomes difficult to form an austenite phase in steel. Therefore, Cr is preferably restricted to the range of 15 35 ma SS %. More preferably, it is 17 mass% and 30 mass%. More preferably, it is 18 mass% and 28 mass%.
- Ni is an element that produces austenite and is also effective in improving crevice corrosion resistance.
- the content thereof, 3 exceeds mas S%, other deteriorate ductility of the Ni amount of the ferrite phase is increased ferrite phase, so causing an increase in cost, preferably 3 mass% or less. More preferably, it is at most 2 mass%.
- the content is preferably 0.1 lmass% or more. L mass% or more is preferable for improving window crevice corrosion.
- N is an element that, like C, increases the austenite phase fraction and is concentrated in the austenite phase to stabilize the austenite phase.
- N exceeds 0.6 ni ass %, blowholes occur during fabrication, making stable production difficult.
- economically disadvantageous means such as pressure melting must be adopted.
- It is preferably set to 0.05 mass% to 0.6 mass%. More preferably, it is 0.1 mass% to 0.4 mass%.
- it is 0.18 mass% or more from the viewpoint of ⁇ phase generation and 0.34 mass% from the viewpoint of hot workability.
- the austenitic / ferritic stainless steel of the present invention can contain OxMo in the following range in addition to the above components.
- Cu 4 mass% or less Cu Cu can be appropriately added to improve corrosion resistance. 0.1 lmass to get that effect. /. The above is preferable. And to force, since more than 4 mass% when hot workability is degradation, preferably limited to 4 ma S s% or less. More preferably, it is 2111 3% or less.
- Mo can be appropriately added to improve corrosion resistance. 0.1 lmass to get that effect. /. The above is preferable. If the force exceeds 4 mass%, the effect is saturated, so it is preferable to limit the effect to 4 mass% or less. It is more preferably at most 21 ⁇ 33 %.
- the stainless steel of the present invention may contain V, Al, B, Ca, Mg, REM and Ti in the following range in addition to the above components.
- ⁇ V 0.5 mass% or less
- V is an element that refines the structure of the steel sheet and increases the strength, and can be added as necessary. 0.005 mass to get the effect. /.
- the above is preferable. However, if it exceeds 0.5 mas S %, the heat treatment temperature for forming a solid solution of C and N becomes extremely high, which causes a decrease in productivity. On the other hand, if it exceeds 0.5 mass S %, it becomes difficult to reduce the precipitation of the V compound even if the annealing temperature is increased, and the overhang formability deteriorates. Therefore, it is preferable to limit the amount of V added to 0.5 mass% or less. It is more preferably at most 0.2 mass%.
- Al is a strong deoxidizing agent and can be added as appropriate. 0.003 mass to get the effect. /.
- the above is preferable. However, if it exceeds 0.1 lmass ° / o, nitrides are formed and may cause surface flaws. Therefore, it is preferable to limit it to 0.1 lmass% or less. It is more preferably at most 0.02 mass%.
- B, Ca, and Mg can be appropriately added as components for improving hot workability.
- 0.0003 mass% or more is preferable. More preferably,
- REM and Ti can be appropriately added as components for improving hot workability. 0.002 mass to get the effect. /. The above is preferable. However, if it exceeds 0.1 lmass%, the corrosion resistance deteriorates. Therefore, it is preferable to limit each to 0.1 lmass% or less. More preferably, it is less than 0.05 mass%.
- the above REM means a rare earth element such as La and Ce.
- Nb can be added as an element to suppress sensitization (deterioration of corrosion resistance due to formation of grain carbides and nitrides at grain boundaries). In order to obtain the effect, 0.01 mass / 0 or more is preferable. However, if it exceeds 2 mas S %, a large amount of Nb carbonitride is generated, and solute C and N in steel are consumed.
- the balance other than the above components is Fe and inevitable impurities.
- O oxygen
- the volume fraction of the austenite phase is set in the range of 10% to 85%, or the C and N contents in the austenitic phase are further reduced to 0.16. mass% to 2 mass. /.
- the lower the Cr, Si, and Mo contents and the higher the C, N, Ni, and Cu contents the higher the austenite phase fraction.
- the annealing temperature is too high, the austenite phase fraction decreases, while if the annealing temperature is too low, C and N precipitate as carbonitrides and the amount of solid solution decreases, contributing to the stabilization of the austenite phase. And the austenite phase fraction also decreases.
- there is a temperature range in which the maximum austenite phase fraction is obtained depending on the steel composition and the temperature is in the range of 700 to 1300 ° C in the composition of the present invention. The longer the annealing time, the closer it is to the equilibrium austenite phase fraction determined by the steel composition and temperature, but it is sufficient to secure about 30 seconds or more.
- the hot-rolled sheet annealing temperature is preferably set in a range of 700 to 1300 ° C.
- the final annealing temperature after cold-rolling is in the range of 700 to 1300 ° C.
- Manufacturing methods other than those described above can be manufactured according to a normal austenitic stainless steel manufacturing method. A specific manufacturing method will be described below.
- the manufacturing method of the steel of the present invention is not limited to the following method.
- the steel After refining using a converter or an electric furnace, the steel is melted by secondary treatment such as VOD (Vacuum Oxygen Decarburization) or AOD (Argon Oxygen Decarburization) as necessary.
- VOD Vauum Oxygen Decarburization
- AOD Aral Oxygen Decarburization
- the melting may be performed in a vacuum or in an atmosphere in which the partial pressure of nitrogen is controlled at 0 to 1 atm.
- the molten steel is made by a known manufacturing method (continuous manufacturing, separation). 5 001555 slab, etc.). The slab is heated to 900 to 1500 ° C. and hot rolled (reverse rolling or unidirectional rolling) into a hot rolled sheet having a desired thickness of 1.5 mm to 10 mm.
- This hot-rolled sheet is annealed at 700 to 1300 ° C if necessary, and then descaled by pickling or the like to obtain a hot-rolled annealed sheet.
- the hot-rolled sheet or the hot-rolled annealed sheet is cold-rolled into a cold-rolled sheet with a thickness of 0.1 to 8 mm.
- annealing, pickling, and cold rolling are repeated once or more times to obtain a desired cold-rolled sheet thickness.
- the cold-rolled sheet is subjected to pickling after annealing at 700 to 1300 ° C. to produce a cold-rolled annealed sheet.
- the volume fraction of the austenite phase of the steel sheet should be in the range of 10% to 85%, or the effects of the present invention can be obtained by adopting the production conditions in which the C and N contents in the tenite phase are in the range of 0.16 mass% to 2 mass%.
- the effects of the present invention can be obtained by any surface finishing condition (No. 2D, No. 2B, BA, polishing finish, etc. specified in JIS G4 305 (2003)). Further, the effect of the present invention can be obtained not only for the above-mentioned rolled plate, but also for wires, pipes, shaped steels and the like.
- the white portion may contain not only the austenite phase but also the martensite phase.However, in the stainless steel of the present invention, since the martensite phase is very small, the value measured by this method is used to calculate the austenite phase fraction. You may use as.
- the white part and the gray part may be reversed. In this case, the austenite phase and the ferrite phase can be distinguished from the austenite phase precipitation form.
- the components in the austenitic phase were analyzed by EPMA. Specifically, C and N have the characteristic of enriching in the austenitic phase, so the qualitative mapping of C or N is performed on the entire cross-section to identify the austenitic phase, and then the electron beam is applied to the ferrite phase. Quantitative analysis of C, N, Si, Mn, Cr, Ni, Cu, and Mo was performed at almost the center of the austenite phase so that the surface was not covered. The measurement area was about ⁇ , and three or more points were measured for each sample, and the average value was used as the representative value. Also, based on these measured values, the following equation (1):
- C (y;), N (r), Si ( 7 ), ⁇ ( ⁇ ), ⁇ ( ⁇ ), ⁇ ( ⁇ ), Cu (y), and ⁇ ( ⁇ ) are the C in the austenite phase, respectively.
- ⁇ Tensile test> JIS No. 13 B tensile test specimens were taken from 0 ° ( ⁇ ), 45 ° and 90 ° with respect to the rolling direction from the cold-rolled annealed sheet, and were subjected to a tensile speed of lOmmZ at room temperature and in air. A tensile test was conducted on the subject. In the tensile test, the total elongation up to the fracture in each direction is measured, and
- ⁇ 1 ⁇ 1 (0 °) + 2 ⁇ 1 (45 °) + E 1 (90.) ⁇ / 4
- Figure 1 shows the effect of the total amount of C and N in the austenite phase and the austenite phase fraction on the total elongation based on the results shown in Table 2. From this, even with the same austenite phase fraction, the steel of the present invention in which the total amount of C and N in the austenite phase is 0.16 to 2 mass%, the total amount of C and N in the austenite phase is less than 0.16 mass%. It shows a higher elongation value than steel, indicating that it has excellent ductility.
- Figure 2 also shows the effect of the work-induced martensite index ( ⁇ (1 ( ⁇ )) on elongation, based on the results in Table 2. From this figure, it can be seen that C and ⁇ in the austenite phase.
- the Md ( ⁇ ) can be further improved by controlling the Md ( ⁇ ) in an appropriate range, and in particular, the Md ( y ) can be controlled in a range of 130 to 90.
- the total elongation was 48% or more (sheet thickness 0.8 mm), indicating that very good ductility characteristics were obtained.
- Figure 3 shows the relationship between the total elongation and the limit drawing ratio (LDR). From FIG. 3, it can be seen that the austenitic / ferritic stainless steel of the present invention has a much higher critical draw ratio than the comparative steel, and is excellent not only in ductility but also in deep drawability.
- LDR limit drawing ratio
- the austenite phase fraction of the hot-rolled sheet was 59% and 57%, respectively, and the amount of C + N in the austenite phase was 0.40 mass%, 0.43 mass%, respectively.
- the total elongations were 58% and 60%, respectively, and the limiting draw ratios were 2.3 and 2.4 ', respectively.
- the austenite phase fraction of the hot-rolled annealed sheet respectively, 6 0%, 5 9% , C + N content of the austenite phase, respectively, 0. 3 9mass%, 0 . 4 2 ma S s%,
- the total elongations were 60% and 61%, respectively, and the limiting draw ratios were 2.4 and 2.4, respectively.
- both the hot-rolled sheet and the hot-rolled annealed sheet showed the same performance as the cold-rolled annealed sheet.
- Table 4 also shows the results of the above measurements.
- Fig. 4 shows the effect of the Ni content in steel, the austenite phase fraction, and the C + N content in the austenite phase on the P gorge reduction ratio. From these results, it satisfies the conditions of the present invention, that is, contains 1 to 3 mass% of Ni and has an austenite phase fraction of 10 to 85 ° /. And in the austenitic phase Austenitic / ferritic stainless steel sheets with a C + N content of 0.116 to 2% all show high values of critical draw ratio of 2.1 or more, indicating that they have excellent deep drawability. .
- C + N content of the austenite phase fraction Contact Yopi austenite phase even within the scope the present invention, the austenite '- full Eraito stainless steel plate Ni content in the steel sheet exceeds 3 mas S%, again limiting drawing ratio Is less than 2.1, indicating that the deep drawability is inferior.
- the austenite phase fraction of the hot-rolled sheet was 81% and 53 %, respectively, and the C + N content in the austenite phase was 0.16 mass% and 0.54 mass%, respectively.
- the austenitic phase fraction of the hot rolled annealed sheet was 79% and 52%, respectively, and the C + N content in the austenitic phase was 0.16 mass% and 0. 53 mass% and the limiting drawing ratio were 2.4 and 2.6, respectively.
- both the hot-rolled sheet and the hot-rolled annealed sheet showed the same performance as the cold-rolled annealed sheet.
- Si is an element effective as a deoxidizing material. In order to obtain the effect, 0.01 mass S % or more is preferable. If the content exceeds 1.2 mAsS %, the hot workability deteriorates. Therefore, when the content is considered to be 1.2 mass% or less, preferably 1.0 mass% or less, and the corrosion resistance deterioration due to sensitization is considered, 0. 4 m a ss% or less.
- Fig. 5 is a graph showing the effect of the Mn content on the stretch formability (Erichsen value) of ferrite-austenitic stainless steel with an M content of 1 mass% or less and an austenite phase fraction of 40 to 50 vol%. It is.
- Mn is a significant impact on bulging formability, it is remarkably improved formability overhang at 2 mas S% or less. The reason The reason is not deterministic and does not affect the extension (range) of the present invention.
- the Mn content is small, the Mn concentration in the ferrite phase is significantly reduced, and as a result, the ductility of the ferrite phase is significantly reduced. To be improved.
- Figure 6 is a graph showing the effect of the Mn content on the results of an outdoor exposure test on a ferrite-austenitic stainless steel with a Ni content of 1 mass% or less and an austenite phase fraction of 40 to 50 vol%. .
- Judgment A was no corrosion
- Judgment B was crevice corrosion
- Judgment C was corrosion both in the crevice and the base metal.
- Mn content is 2 m ass% or less, good crevice corrosion resistance is obtained. The reason is not definitive and does not affect the extension (range) of the present invention. However, when the Mn content is low, inclusions such as MnS that adversely affect the corrosion resistance of the crevice area may be reduced. Decrease.
- the Mn content should be 2 mass% or less, and preferably 1.5 mass% or less, in order to obtain sufficient properties with respect to stretch formability and crevice corrosion resistance. Limited.
- Ni is an element that promotes the formation of an austenite phase.
- the content is preferably not less than 0. oi mass %.
- the content is high, excellent overhang formability cannot be obtained.
- SUS329-based ferritic austenitic stainless steel contains about 50% of austenite phase, but when Ni content exceeds l mass%, stretch formability is significantly deteriorated.
- Ni is an expensive alloy element, and its content is required to be reduced as much as possible from the viewpoints of economics and resource saving to the extent necessary to generate a ferrite-austenite structure. From such a viewpoint, the Ni content is limited to 1 mass% or less, and preferably 0.9 mass% or less. However, if the Ni content is 0.10 mass% or less, the toughness of the steel decreases in both the base metal and the weld. Therefore, the Ni content is most preferably more than 0.10 mass% and 0.9 mass% or less.
- the steel according to the present invention needs to be a ferritic / austenite stainless steel having the above composition and a metal structure having an austenite phase fraction of 10 vol% or more and 85 vol% or less in the structure.
- Fig. 7 is a graph showing the relationship between the austenite phase fraction and the stretch formability (Erichsen value) of a ferritic austenitic stainless steel sheet with a Mn content of 2 mass% or less and a Ni content of 1 mass% or less. is there. As shown here, the overhang ⁇ improved with an increase in the austenite phase fraction,
- the austenite phase fraction is limited to 10 to 85 vol%, preferably 15 to 85 vol%.
- Ferritic and austenitic stainless steels having the above basic composition and having an austenite phase fraction in the metal structure of ⁇ / ⁇ or more and 85 vol% or less are relatively inexpensive and conserve Ni resources. It is excellent in overhang formability and crevice corrosion resistance.
- the amount of C + N contained in the austenite phase of the steel structure is 0.16 mass% or more. It is preferably set to not more than mass%.
- C + N content is 0. 16 m a ss% In ⁇ sufficient ductility contained in austenitic phase of the steel organization, not deep drawability is obtained, whereas, difficult to contain in excess of 2 ma SS% Because there is. More preferably, it is contained in the range of 0.2 mass% to 2 mass%.
- the amounts of C and N in the austenite phase can be adjusted by adjusting the composition of the steel and the annealing conditions (temperature and time).
- the relationship between the steel structure and the annealing conditions and the amount of (:, N in the austenite phase cannot be generalized.
- the amount of Cr, C, and N in steel and tissue is high, the (: In many cases, when the composition of steel is the same, the lower the austenite phase fraction determined by the annealing conditions, the higher the (:, N content) in the austenite phase.
- the measurement of C and N contents in the austenite phase should be performed by EPMA, for example. Can be. 1555 Example 3
- the measurement of the austenite phase fraction was performed in the same manner as in Example 1.
- the stretch formability was determined by the Erichsen test, and the punch-in length until cracking occurred was defined as the Erichsen value.
- the test piece was a square plate with dimensions of 80 mm x 80 mm, coated with graphite grease and lubricated.
- the test was performed under the conditions of a punch diameter of 20 mm and a wrinkle holding force of 15.7 kN. Other conditions were according to JIS Z 2 247 Erichsen test. Also, as shown in Fig.
- the crevice resistance corrosion test was performed on a cold-rolled annealed sheet of 8 cm wide x 12 cm long with the surface scale removed, 3 cm wide x 4.5 cm with the same material scale removed.
- a long cold-rolled annealed plate is piled up (small plate), and these are tightly fixed with Teflon (registered trademark) bolts and Teflon (registered trademark) washers, and are about 0.7 km from the coast for 7 months.
- Teflon registered trademark
- Teflon registered trademark
- the ferritic / austenitic stainless steel sheet satisfying the present invention had an Erichsen value of 12 mm or more, had high stretch formability, and showed no gap-resistant portion even in the exposure test.
- the evaluation of the corrosion resistance in the gaps was made when the mark ⁇ was not corroded and the mark X was corroded.
- Table 6B shows the results of evaluating the stretch formability and the crevice corrosion resistance of the steel sheets Nos. 1 to 4 of the steel sheets of Tables 1 and 2 of Example 1 in the same manner as in the above example. This shows that not only the formability shown in Table 2 but also a steel sheet excellent in stretch formability and crevice corrosion resistance was obtained.
- hot-rolled sheet (finish temperature) is a steel sheet excellent in stretch formability and crevice corrosion resistance.
- austenite phase fraction, stretch formability, crevice corrosion resistance was measured.
- austenite phase fraction of the hot-rolled sheet was 48% and 45%, respectively, and the Erichsen values were 14.5 mm and 14.0 mm, respectively.
- the austenite phase fraction of the hot-rolled annealed sheet was respectively , 47%, 44% (please add specific values) and Erichsen values were 14.6mm and 14.2mm, respectively.
- no corrosion was observed in any of the base material and the gap between the hot-rolled sheet and the hot-rolled annealed sheet.
- the performances of the hot-rolled sheet and the hot-rolled annealed sheet were similar to those of the cold-rolled annealed sheet.
- Si is an element effective as a deoxidizing material. In order to obtain the effect, 0.01 mass% or more is preferable. If the content exceeds 1.2 mass%, the hot workability deteriorates, so the content is limited to 1.2 mass% or less, preferably 1.0 mass% or less. In order to further suppress the deterioration of corrosion resistance due to sensitization, the Si content is preferably set to 0.4 ma SS ° / o or less.
- Mn is a particularly important element for obtaining excellent weld corrosion resistance.
- Figure 9 shows that the welding test material, including the weld, the heat-affected zone and the base metal, was held at a potential of 100-300 mV V s SCE for 30 min in a 0.035% (mass ratio) sodium chloride solution. It is a graph showing the relationship between the presence or absence of corrosion and the Mn content. The presence or absence of corrosion was judged as “corrosion” when the current value was 1 mA or more, and as “no corrosion” when the current value was less than 1 mA.
- the amount of Mn is limited to 4 mass% to 12 mass%, preferably 5.2 mass% to 10 mass%, and more preferably less than 6.8 mass%.
- Ni is an austenite formation promoting element and is useful for forming ferrite 'austenitic yarns and fibers'. 0. Olmass to get the effect. /.
- the above is preferable. However, it is an expensive alloying element and needs to be reduced as much as possible to conserve resources. From these viewpoints, the Ni content is limited to 1 mass% or less, preferably 0.9 mass% or less. However, if the Ni content is 0.10 mass% or less, the toughness of the base metal and the weld decreases. Therefore, in order to improve the toughness including the welded portion, it is preferable that M is contained at least in an amount of more than 0.10 mass% (see Example 6). 2005/001555 FIG.
- FIG. 10 is a graph showing the effect of the austenite phase fraction on the corrosion resistance of the welded material including the base metal.
- the method of measuring the corrosion resistance is the same as in FIG.
- the austenite phase fraction exceeds ⁇ / ⁇ , the corrosion resistance of the welded portion is significantly improved.
- ferrite-austenitic stainless steels with a low Ni content and a high N content have a high diffusion rate of N at the time of cooling after welding, so that chromium nitride is formed at the grain boundaries including the ferrite phase. It is thought that chromium-depleted regions are likely to occur due to the precipitation.
- ferritic austenitic stainless steels having an austenite phase of 10 vol% or more, especially 15 vol% or more as in the present invention Cr is reduced at the grain boundaries including the ferrite phase due to high austenite phase forming ability. Even so, the part transforms into an austenitic phase, increasing the solubility of chromium nitride, and consequently reducing the chromium-depleted region.
- the austenite phase fraction exceeds 85 vol%, the susceptibility to stress corrosion cracking increases significantly.
- the austenite phase fraction is set to 10 to 85 vol%, preferably 15 to 85 vol%.
- the ferrite 'austenitic stainless steel of the present invention should contain 0.16 mass% or more of C + N contained in the austenitic phase of the steel structure. It is preferable to be 2 mass% or less. In C + N quantity sufficient ductility is less than 0. 16 mass% contained in the O austenite phase of the steel structure, not deep drawability is obtained, whereas, since the content exceeds 2 ma SS% is difficult is there. Preferably, it is contained in the range of 0.2 mass% to 2 mass%.
- the amounts of C and N in the austenite phase can be adjusted by adjusting the composition of the steel and the annealing conditions (temperature and time).
- the relationship between the steel structure and annealing conditions and the amount of (, N) in the austenite phase cannot be generalized, but when the Cr, C, and N contents in the steel structure are large, the C and N contents in the austenite phase increase.
- the composition of steel is the same, the lower the austenite phase fraction determined by the annealing conditions, the lower the PT / JP2005 / 001555
- An appropriate amount of (:, N can be included based on empirically obtained knowledge such as the fact that the amount of (, N in the austenite phase often increases.
- the content of C and N in the phase can be measured by, for example, EPMA.
- the corrosion resistance test of the welded part was performed by grinding the surface scale of a test piece 25 mm on a side including the obtained weld bead, heat-affected zone and base material, and grinding it to 0.035% (mass ratio) aqueous sodium chloride solution.
- the sample was held at 100, 200 and 300 mV vs SCE for 30 minutes, and the sample with current of 1 mA or more was evaluated as ⁇ corrosion '', and the sample without current of 1 mA or more was evaluated as ⁇ no corrosion ''. evaluated.
- the test results are shown in Table 9A.
- Table 9A In Table 9A, ⁇ indicates “no corrosion” and X indicates “corrosion”. It is clear that the welding material of the steel of the present invention does not corrode up to a potential of 200 mV Vs S C E. And has excellent corrosion resistance at the welded portion.
- Table 9B shows the results of evaluating the corrosion resistance of the welded portions of the steel sheets Nos. 12 to 29 of the steel sheets of Tables 1 and 2 of Example 1 in the same manner as in the above Examples. This shows that not only the formability shown in Table 2 but also a steel sheet excellent in the corrosion resistance of the weld was obtained.
- Example 10 a steel having the composition shown in Table 10 was melted and formed into a steel strip (or steel ingot, ingot), heated at 125 ° C, and then hot-rolled ( 1 to 11 passes with a plate thickness of 4 to 6 arms), annealing (1100 for lmin), cold rolling (room temperature to 300 ° C, then cold rolling), then a temperature of 1050 ° C Finish annealing was performed to obtain a cold-rolled annealed sheet with a thickness of 2.25 mm. The austenite phase fraction was measured for the obtained cold-rolled annealed sheet. The measurement of the austenite phase fraction was performed in the same manner as in Example 1.
- a TIG welding machine place a welding bead with a width of about 5 mm at right angles to the rolling direction on the cold-rolled sheet obtained above using a TIG welding machine at a power of 900 W and a speed of 30 cm / min.
- a 10 mm wide and 75 mm long test piece parallel to the rolling direction from the weld was used as a U-bend test piece with a bending radius of 10 mm.
- the bottom of the U-bend specimen was used as the weld.
- the U-bend test piece prepared in this way was immersed in a 42 mass% magnesium chloride aqueous solution (temperature: 80 ° C), and the presence or absence of cracks was visually inspected every 24 hours.
- the survey results are shown in Table 11. As is clear from Table 5, when the C content is less than 0.1%, the stress corrosion cracking resistance of the base metal welded portion is remarkably improved.
- Example 12 a steel having the composition shown in Table 12 was melted and formed into a steel slab (or steel ingot, ingot), and then heated at 125 ° C, and then hot-rolled. (10 to 11 passes with a plate thickness of 4 to 6 bars), annealing (1min at 110 ° C), cold rolling (cold rolling after heating from room temperature to 300 ° C), and then 1050 ° C Finished annealing at a temperature of 2.25 mm cold-rolled annealed sheet Got.
- the austenite phase fraction was measured for the obtained cold-rolled annealed sheet.
- the structure observation (measurement of austenite phase fraction) was performed in the same manner as in Example 1.
- a welding bead having a width of about 5 mm was placed in a direction perpendicular to the rolling direction on the cold-rolled sheet obtained above under the conditions of an input power of 900 W and a speed of 30 cm / min.
- a Charvy impact test piece was cut out with a 2 mm V notch perpendicular to the rolling direction, and an impact test was performed at 0 ° C.
- Table 13 shows the results of the impact test. As is evident from Table 13, by setting the Ni content to 0.1% or more, the impact absorption energy of the base metal weld is significantly improved.
- the steel according to the present invention is a steel having the composition described in (1) above (C: 0.2 ma SS % or less, Si: 4 mass 0 / 0 or less, Mn: 12 mass% or less, P: 0.0 lmass% or less, S: 0.03 mass% or less, Cr: 15 mass% to 35 mass%, Ni: 3 mass% or less, N: 0.05 mass% to 0 Steel containing 6 mass%, the balance being Fe and unavoidable impurities, or steel containing one or two of the following: Mo: 4 111335% or less, Cu: 4 mass% or less. Further, steel containing V of 0.5 mass ° / o or less, or steel containing A1 of 0.1 mass% or less, or B: 0.01 mass% or less, and Ca: 0.01 mass% or less , Mg:
- the austenite phase fraction should be 10 to 85% by volume in the whole structure.
- Si is an element effective as a deoxidizing material, and can be added as appropriate. In order to obtain the effect, 0.01 mass% or more is preferable. However, when the amount of Si exceeds 0.4 ma SS ° / o, the solid solubility of N decreases. Therefore, the deterioration of corrosion resistance due to the sensitization described in the background art is scattered. Therefore, the amount of Si is set to 0.4 mass% or less, preferably 0.38 mass% or less.
- Mn enhances the solubility of N when it exceeds 2 mass%, facilitating the addition of N during steelmaking. At the same time, the addition of Mn increases the ⁇ phase fraction. However, above 4 mass%, the effect of generating the ⁇ phase saturates. Therefore, it is more than 2 mas S % and less than 4 mass%. A preferred range is 2.2 mass% or more and 3.8 mass% or less. '
- Ni content is limited to 1 maSS % or less for economical reasons and Ni resource conservation. Preferably, it is 0.9% or less. In order to obtain excellent toughness, 0.1 mass% or more is preferable.
- the austenite phase fraction should be 10% or more and 85% or less, preferably 15% or more and 80%.
- the ferrite-austenite stainless steel of the present invention should contain 0.16 fflass% or more of C + N contained in the austenite phase of the steel structure. It is preferably set to not more than mass%.
- the amount of C + N contained in the austenite phase of the steel tissue is less than 0.16 mass%, sufficient ductility and deep drawability cannot be obtained, while it is difficult to contain more than 2 mASS %. is there. It is more preferable that the content be contained in the range of 0.2 to 2 mass%.
- the amounts of C and N in the austenite phase can be adjusted by adjusting the composition of the steel and the annealing conditions (temperature and time).
- the relationship between the steel structure and the annealing conditions and the amount of (:, N) in the austenite phase cannot be generalized. However, when the amount of Cr and N in the steel structure is large, the amount of N in the austenite phase may increase. If the composition of steel is the same, the empirical results show that the lower the austenite phase fraction determined by the annealing conditions, the higher the amount of (:, N) in the austenite phase is, the empirically obtained. Knowledge gained Based on 5 001555, appropriate amounts of C and N can be contained.
- the C and N contents in the austenite phase can be measured by, for example, EPMA.
- Microstructure observation and corrosion resistance measurement were performed on the prepared cold-rolled annealed sheet. The results obtained are also shown in Table 14A.
- the structure observation (measurement of austenite phase ((phase) fraction) was performed in the same manner as in Example 1.
- the method for measuring and evaluating the intergranular corrosion resistance is as follows.
- the surface of the cold-rolled annealed plate was polished with Emery # 300 and evaluated.
- Test solution Add 100 mg of copper sulfate pentahydrate and 100 ml of sulfuric acid to water and add 100 mg
- Test method The test piece is immersed in the above boiling solution for 8 hours.
- Bending was performed at a bending angle of 5 ° and a bending angle of 90 °.
- Table 14B shows the results of evaluating the intergranular corrosion resistance of steel sheets Nos. 5 to 8 of the steel sheets of Tables 1 and 2 of Example 1 in the same manner as in the above-mentioned Examples. It is shown that not only the formability shown in Table 2 but also a steel sheet excellent in intergranular corrosion resistance was obtained for all steel sheets.
- hot-rolled sheet hot-rolled to 4.5 strokes finish temperature 1000 ° C
- hot-rolled annealed at 1050 ° C for 1 minute The austenitic phase fraction and intergranular corrosion resistance were measured and evaluated for the sheet in the same manner as for the cold-rolled annealed sheet described above.
- the austenite phase fraction of the hot-rolled sheet was 60% and 60%, respectively, and the austenite phase fraction of the hot-rolled annealed sheet was 58% and 59%, respectively.
- the austenite phase fraction of the hot-rolled annealed sheet was 58% and 59%, respectively.
- both the hot-rolled sheet and the hot-rolled annealed sheet showed the same performance as the cold-rolled annealed sheet.
- the technology related to austenitic / ferritic stainless steel of the present invention is not limited to steel plates.For example, even when applied to thick plates, section steels, wire rods, pipes, etc., the conditions of the present invention should be satisfied. As a result, in addition to excellent ductility and deep drawability, excellent overhanging properties, crevice corrosion, excellent weld corrosion resistance, and excellent grain boundary corrosion resistance can be obtained.
- steel sheet of the present invention can be suitably used as a material for automobile members, kitchen equipment, building hardware and the like.
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Abstract
Description
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EP05709655.4A EP1715073B1 (en) | 2004-01-29 | 2005-01-27 | Austenitic-ferritic stainless steel |
US10/587,222 US8562758B2 (en) | 2004-01-29 | 2005-01-27 | Austenitic-ferritic stainless steel |
CN2005800037293A CN1914344B (zh) | 2004-01-29 | 2005-01-27 | 奥氏体-铁素体类不锈钢 |
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EP (2) | EP2562285B1 (ja) |
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DE102015112215A1 (de) * | 2015-07-27 | 2017-02-02 | Salzgitter Flachstahl Gmbh | Hochlegierter Stahl insbesondere zur Herstellung von mit Innenhochdruck umgeformten Rohren und Verfahren zur Herstellung derartiger Rohre aus diesem Stahl |
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CN114934240B (zh) * | 2022-04-25 | 2023-10-10 | 中国科学院金属研究所 | 一种超高强高耐蚀高氮奥氏体不锈钢的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5651222B1 (ja) * | 1970-12-23 | 1981-12-03 | ||
JPH01225754A (ja) * | 1988-02-04 | 1989-09-08 | Armco Advanced Materials Corp | 二重溶解高マンガンステンレス鋼 |
JPH1171643A (ja) * | 1997-06-30 | 1999-03-16 | Union Sider Nord Est Fr <Usinor> | 引張り延びに優れたニッケル含有率が極めて低いオーステノ・フェライト系ステンレス鋼 |
JP2002194511A (ja) * | 2000-12-14 | 2002-07-10 | Caterpillar Inc | 優れた高温強度及び延性を備える耐熱性及び耐腐食性ステンレス鋳鋼 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3861908A (en) * | 1973-08-20 | 1975-01-21 | Crucible Inc | Duplex stainless steel |
JPS5651222A (en) | 1979-03-22 | 1981-05-08 | Mitsubishi Heavy Ind Ltd | Wet type gas treatment device of spray mode |
US4721600A (en) * | 1985-03-28 | 1988-01-26 | Sumitomo Metal Industries, Ltd. | Superplastic ferrous duplex-phase alloy and a hot working method therefor |
FR2630132B1 (fr) * | 1988-04-15 | 1990-08-24 | Creusot Loire | Acier inoxydable austeno-ferritique |
JPH0768603B2 (ja) | 1989-05-22 | 1995-07-26 | 新日本製鐵株式会社 | 建築建材用二相ステンレス鋼 |
US5254184A (en) * | 1992-06-05 | 1993-10-19 | Carpenter Technology Corporation | Corrosion resistant duplex stainless steel with improved galling resistance |
JP2861720B2 (ja) * | 1993-03-02 | 1999-02-24 | 日本鋼管株式会社 | 強度、靱性および耐食性に優れた2相ステンレス溶接鋼管の製造方法 |
CA2123470C (en) * | 1993-05-19 | 2001-07-03 | Yoshihiro Yazawa | Ferritic stainless steel exhibiting excellent atmospheric corrosion resistance and crevice corrosion resistance |
SE501321C2 (sv) * | 1993-06-21 | 1995-01-16 | Sandvik Ab | Ferrit-austenitiskt rostfritt stål samt användning av stålet |
JP2933826B2 (ja) | 1994-07-05 | 1999-08-16 | 川崎製鉄株式会社 | 深絞り成形性と耐二次加工脆性に優れるクロム鋼板およびその製造方法 |
JP2910659B2 (ja) * | 1996-01-31 | 1999-06-23 | 三菱マテリアル株式会社 | ディーゼルエンジン用副燃焼室口金 |
JP3463500B2 (ja) * | 1997-02-07 | 2003-11-05 | Jfeスチール株式会社 | 延性に優れたフェライト系ステンレス鋼およびその製造方法 |
JP2000239799A (ja) | 1999-02-19 | 2000-09-05 | Daido Steel Co Ltd | Niを含まない生体用二相ステンレス鋼 |
JP3508095B2 (ja) * | 1999-06-15 | 2004-03-22 | 株式会社クボタ | 耐熱疲労性・耐腐食疲労性およびドリル加工性等に優れたフェライト−オーステナイト二相ステンレス鋼および製紙用サクションロール胴部材 |
ES2182647B1 (es) * | 2000-08-07 | 2003-12-16 | Acerinox Sa | Acero inoxidable duplex austeno-ferritico con bajo contenido en niquel. |
SE517449C2 (sv) * | 2000-09-27 | 2002-06-04 | Avesta Polarit Ab Publ | Ferrit-austenitiskt rostfritt stål |
DE10215598A1 (de) * | 2002-04-10 | 2003-10-30 | Thyssenkrupp Nirosta Gmbh | Nichtrostender Stahl, Verfahren zum Herstellen von spannungsrißfreien Formteilen und Formteil |
-
2005
- 2005-01-27 EP EP12191121.8A patent/EP2562285B1/en active Active
- 2005-01-27 WO PCT/JP2005/001555 patent/WO2005073422A1/ja not_active Application Discontinuation
- 2005-01-27 US US10/587,222 patent/US8562758B2/en active Active
- 2005-01-27 KR KR1020087031469A patent/KR20090005252A/ko not_active Application Discontinuation
- 2005-01-27 CN CN2005800037293A patent/CN1914344B/zh active Active
- 2005-01-27 EP EP05709655.4A patent/EP1715073B1/en active Active
- 2005-01-27 KR KR1020067015346A patent/KR100957664B1/ko active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5651222B1 (ja) * | 1970-12-23 | 1981-12-03 | ||
JPH01225754A (ja) * | 1988-02-04 | 1989-09-08 | Armco Advanced Materials Corp | 二重溶解高マンガンステンレス鋼 |
JPH1171643A (ja) * | 1997-06-30 | 1999-03-16 | Union Sider Nord Est Fr <Usinor> | 引張り延びに優れたニッケル含有率が極めて低いオーステノ・フェライト系ステンレス鋼 |
JP2002194511A (ja) * | 2000-12-14 | 2002-07-10 | Caterpillar Inc | 優れた高温強度及び延性を備える耐熱性及び耐腐食性ステンレス鋳鋼 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1715073A4 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI463020B (zh) * | 2006-06-16 | 2014-12-01 | Industeel Creusot | 雙重不銹鋼 |
US20150167135A1 (en) * | 2006-06-16 | 2015-06-18 | Industeel Creusot | Duplex stainless steel |
WO2009048137A1 (ja) | 2007-10-10 | 2009-04-16 | Nippon Steel & Sumikin Stainless Steel Corporation | 2相ステンレス鋼線材、鋼線およびボルト並びにその製造方法 |
US8858872B2 (en) | 2007-11-29 | 2014-10-14 | Ati Properties, Inc. | Lean austenitic stainless steel |
US10370748B2 (en) | 2007-11-29 | 2019-08-06 | Ati Properties Llc | Lean austenitic stainless steel |
US9617628B2 (en) | 2007-11-29 | 2017-04-11 | Ati Properties Llc | Lean austenitic stainless steel |
US9133538B2 (en) | 2007-12-20 | 2015-09-15 | Ati Properties, Inc. | Lean austenitic stainless steel containing stabilizing elements |
US9121089B2 (en) | 2007-12-20 | 2015-09-01 | Ati Properties, Inc. | Lean austenitic stainless steel |
US9624564B2 (en) | 2007-12-20 | 2017-04-18 | Ati Properties Llc | Corrosion resistant lean austenitic stainless steel |
US9822435B2 (en) | 2007-12-20 | 2017-11-21 | Ati Properties Llc | Lean austenitic stainless steel |
US9873932B2 (en) | 2007-12-20 | 2018-01-23 | Ati Properties Llc | Lean austenitic stainless steel containing stabilizing elements |
US10323308B2 (en) | 2007-12-20 | 2019-06-18 | Ati Properties Llc | Corrosion resistant lean austenitic stainless steel |
US8877121B2 (en) | 2007-12-20 | 2014-11-04 | Ati Properties, Inc. | Corrosion resistant lean austenitic stainless steel |
Also Published As
Publication number | Publication date |
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KR20060127107A (ko) | 2006-12-11 |
US20070163679A1 (en) | 2007-07-19 |
EP2562285B1 (en) | 2017-05-03 |
CN1914344A (zh) | 2007-02-14 |
US8562758B2 (en) | 2013-10-22 |
EP1715073B1 (en) | 2014-10-22 |
CN1914344B (zh) | 2011-06-01 |
EP1715073A4 (en) | 2007-09-26 |
EP2562285A1 (en) | 2013-02-27 |
EP1715073A1 (en) | 2006-10-25 |
KR20090005252A (ko) | 2009-01-12 |
KR100957664B1 (ko) | 2010-05-12 |
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