EP3524705B1 - Ni-cr-fe alloy - Google Patents
Ni-cr-fe alloy Download PDFInfo
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- EP3524705B1 EP3524705B1 EP17858416.5A EP17858416A EP3524705B1 EP 3524705 B1 EP3524705 B1 EP 3524705B1 EP 17858416 A EP17858416 A EP 17858416A EP 3524705 B1 EP3524705 B1 EP 3524705B1
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- alloy
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- nicrfe
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- 229910000640 Fe alloy Inorganic materials 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims description 165
- 239000000956 alloy Substances 0.000 claims description 165
- 150000002910 rare earth metals Chemical class 0.000 claims description 67
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 66
- 239000000126 substance Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 14
- 238000005097 cold rolling Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 description 59
- 230000035882 stress Effects 0.000 description 40
- 238000005336 cracking Methods 0.000 description 38
- 230000000694 effects Effects 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000002244 precipitate Substances 0.000 description 23
- 230000032683 aging Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000010955 niobium Substances 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 239000011575 calcium Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 12
- 229910001566 austenite Inorganic materials 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000002542 deteriorative effect Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000001747 exhibiting effect Effects 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- 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
Definitions
- the present invention relates to an austenitic heat resistant alloy, and more specifically a NiCrFe alloy.
- facilities such as thermal power generation boilers and chemical plants are operated in high temperature environments (such as 400 to 800°C) and, in addition, they are brought into contact with process fluids including sulfides and/or chlorides. Therefore, materials to be used in such facilities require their creep strength and corrosion resistance at high temperatures.
- Examples of the material for use in such facilities include 18-8 stainless steel such as SUS304H, SUS316H, SUS321H, and SUS347H, and NiCrFe alloys represented by Alloy 800H, which is specified as NCF800H by the JIS standard.
- a NiCrFe alloy excels in corrosion resistance and high temperature strength compared to an 18-8 stainless steel. Further, a NiCrFe alloy excels in economic efficiency compared to a Ni-base alloy represented by Alloy617. Therefore, NiCrFe alloys are widely used in regions of severe use environments.
- Patent Literature 1 Japanese Patent Application Publication No. 2013-227644
- Patent Literature 2 Japanese Patent Application Publication No. 06-264169
- Patent Literature 3 Japanese Patent Application Publication No. 2002-256398
- Patent Literature 4 Japanese Patent Application Publication No. 08-13104
- a heat resistant and corrosion resistant alloy disclosed in Patent Literature 2 consists of, in weight%, 55 to 65% of Nickel, 19 to 25% of Chromium, 1 to 4.5% of Aluminum, 0.045 to 0.3% of Yttrium, 0.15 to 1% of Titan, 0.005 to 0.5% of Carbon, 0.1 to 1.5% of Silicon, not more than 1% of Manganese, a total of 0.005% of at least one element selected from the group consisting of Magnesium, Calcium, and Cerium, a total of less than 0.5% of Magnesium and Calcium, less than 1% of Cerium, 0.0001 to 0.1% of Boron, not more than 0.5% of Zirconium, 0.0001 to 0.2% of Nitrogen, and not more than 10% of Cobalt, with the balance being Fe and accompanying impurities.
- An austenitic alloy disclosed in Patent Literature 3 contains, in mass%, C: 0.01 to 0.1%, Mn: 0.05 to 2%, Cr: 19 to 26%, and Ni: 10 to 35%, with the Si content satisfying a formula of 0.01 ⁇ Si ⁇ (Cr + 0.15 ⁇ Ni - 18)/10.
- a heat resistant alloy disclosed in Patent Literature 4 consists of, in weight%, C: 0.02 to 0.15%, Si: 0.70 to 3.00%, Mn: not more than 0.50%, Ni: 30.0 to 40.0%, Cr: 18.0 to 25.0%, Al: 0.50 to 2.00%, and Ti: 0.10 to 1.00%, with the balance being Fe and inevitable impurities. Further, also Patent Application Publication US2010/034690 discloses an austenitic NiCrFe-alloy.
- Non Patent Literature 1 Hans van Wortel: “Control of Relaxation Cracking in Austenitic High Temperature Components", CORROSION2007 (2007), NACE, Paper No.07423
- the austenitic heat resistant alloy disclosed in Patent Literature 1 controls the formation of Laves phase by specifying the contents of W, Mo, Nb, and Ti, thereby improving creep strength and toughness.
- the heat resistant and corrosion resistant alloy disclosed in Patent Literature 2 improves high-temperature oxidation resistance by causing ⁇ ' to be precipitated during creep.
- the austenitic alloy disclosed in Patent Literature 3 improves carburizing properties by suppressing exfoliation of the oxide film dominantly composed of Cr 2 O 3 and formed on the material surface.
- the heat resistant alloy disclosed in Patent Literature 4 contains a specific amount of Cr, a reduced amount of Mn, and a fixed amount of Si, thereby making it possible to obtain excellent oxidation resistance even in a case in which the Ni content is reduced.
- Non Patent Literature 1 discloses that a NiCrFe alloy has a high susceptibility to stress relaxation cracking. This means that a NiCrFe alloy requires stress relief heat treatment, after working, for a bent part and welded part, in which residual stress is present. Therefore, a NiCrFe alloy requires not only excellent creep strength but also excellent stress relaxation cracking resistance.
- An objective of the present invention is to provide a NiCrFe alloy which excels in creep strength and stress relaxation cracking resistance.
- a NiCrFe alloy according to the present invention has a chemical composition consisting of, in mass%, C: 0.03 to 0.15%, Si: not more than 1.00%, Mn: not more than 2.00%, P: not more than 0.040%, S: not more than 0.0050%, Cr: 18.0 to 25.0%, Ni: 25.0 to 40.0%, Ti: 0.10 to 1.60%, Al: 0.05 to 1.00%, N: not more than 0.020%, O: not more than 0.008%, rare earth metal (REM): 0.001 to 0.100%, B: 0 to 0.010%, Ca: 0 to 0.010%, Mg: 0 to 0.010%, V: 0 to 0.5%, Nb: 0 to 1.0%, Ta: 0 to 1.0%, Hf: 0 to 1.0%, Mo: 0 to 1.0%, W: 0 to 2.0%, Co: 0 to 3.0%, and Cu: 0 to 3.0%, with the balance being Fe and impurities, the chemical composition satisfying Formulae (1) to (3)
- a NiCrFe alloy according to the present invention excels in creep strength and stress relaxation cracking resistance.
- FIG. 1 is a diagram to show a relation between fn2 of each Reference mark of Examples, and a sum (mass%) of ⁇ ' and ⁇ phase after aging treatment.
- the present inventors have conducted detailed study on the creep strength and the stress relaxation cracking resistance of NiCrFe alloys. As a result, the present inventors have obtained the following findings.
- adjusting the content of REM to be an appropriate amount will allow improving the stress relaxation cracking resistance of the NiCrFe alloy.
- REM combines with S and is also likely to combine with O easily. Therefore, to immobilize S by REM, the REM content should be adjusted while the amount of REM that combines with O is taken into consideration.
- ⁇ [REM/(A(REM))] is substituted by an addition sum of values which are obtained by dividing each REM content (mass%) contained in the NiCrFe alloy by the atomic weight of the REM.
- fn3 ⁇ [REM/(A(REM))] - S/32 - 2/3•O/16.
- REM is a generic name of a total of 17 elements of Sc, Y, and lanthanoids.
- fn3 is not less than 0, REM can sufficiently immobilize S as inclusions, thereby improving the stress relaxation cracking resistance.
- the NiCrFe alloy according to the present invention which has been completed based on the above described findings, has a chemical composition consisting of, in mass%, C: 0.03 to 0.15%, Si: not more than 1.00%, Mn: not more than 2.00%, P: not more than 0.040%, S: not more than 0.0050%, Cr: 18.0 to 25.0%, Ni: 25.0 to 40.0%, Ti: 0.10 to 1.60%, Al: 0.05 to 1.00%, N: not more than 0.020%, O: not more than 0.008%, rare earth metal (REM): 0.001 to 0.100%, B: 0 to 0.010%, Ca: 0 to 0.010%, Mg: 0 to 0.010%, V: 0 to 0.5%, Nb: 0 to 1.0%, Ta: 0 to 1.0%, Hf: 0 to 1.0%, Mo: 0 to 1.0%, W: 0 to 2.0%, Co: 0 to 3.0%, and Cu: 0 to 3.0%, with the balance being Fe and im
- the above described chemical composition may contain B: 0.0001 to 0.010%.
- the above described chemical composition may contain one or two types selected from the group consisting of Ca: 0.0001 to 0.010%, and Mg: 0.0001 to 0.010%.
- the above described chemical composition may contain one or more types selected from the group consisting of V: 0.01 to 0.5%, Nb: 0.01 to 1.0%, Ta: 0.01 to 1.0%, and Hf: 0.01 to 1.0%.
- the above described chemical composition may contain one or more types selected from the group consisting of Mo: 0.01 to 1.0%, W: 0.01 to 2.0%, Co: 0.01 to 3.0%, and Cu: 0.01 to 3.0%.
- the NiCrFe alloy according to the present invention has excellent creep strength and excellent stress relaxation cracking resistance. To be more specific, the NiCrFe alloy will not rupture for 300 or more hours even if it is subjected to tensile strain of 10% at a strain rate of 0.05 min -1 and is kept as is under air atmosphere of 650°C after being subjected to cold rolling at a reduction of area of 20%.
- the chemical composition of NiCrFe alloy of the present invention contains the following elements.
- C content is 0.03 to 0.15%.
- the lower limit of the C content is preferably 0.04%, more preferably more than 0.04%, and further preferably 0.05%, and further preferably 0.06%.
- the upper limit of the C content is preferably 0.12%, and more preferably 0.10%.
- Si Silicon
- Si is inevitably contained. Si deoxidizes the alloy, and improves the corrosion resistance and oxidation resistance at high temperatures of the alloy. However, when the Si content is too high, the stability of austenite deteriorates, and toughness and creep strength of the alloy decrease. Therefore, the Si content is not more than 1.00%.
- the upper limit of the Si content is preferably 0.80%, more preferably 0.60%, and further preferably less than 0.60%. Excessive reduction of the Si content deteriorates deoxidization effect, thus deteriorating the corrosion resistance and oxidization resistance at high temperatures of the alloy. And further, the production cost is significantly increased. Therefore, the lower limit of the Si content is preferably 0.02%, and more preferably 0.05%.
- Mn Manganese
- the upper limit of the Mn content is preferably 1.80%, and more preferably 1.50%. Excessive reduction of the Mn content deteriorates the deoxidization effect and stabilization of austenite, and further causes significant increase of the production cost. Therefore, the lower limit of the Mn content is preferably 0.10%, more preferably 0.30%, and further preferably more than 0.50%.
- Phosphorous (P) is an impurity. P deteriorates hot workability and weldability of the alloy, and also deteriorates creep ductility of the alloy after long hours of usage. Therefore, the P content is not more than 0.040%.
- the upper limit of the P content is preferably 0.035%, and more preferably 0.030%.
- the P content is preferably as low as possible. However, excessive reduction of the P content will increase the production cost. Therefore, the lower limit of the P content is preferably 0.0005%, and more preferably 0.0008%.
- S Sulfur
- S is an impurity. S deteriorates the stress relaxation cracking resistance of the alloy, and also deteriorates the hot workability, weldability, and creep ductility of the alloy. Therefore, the S content is not more than 0.0050%.
- the upper limit of the S content is preferably 0.0030%.
- the S content is preferably as low as possible. However, excessive reduction of the S content will increase the production cost. Therefore, the lower limit of the S content is preferably 0.0002%, and more preferably 0.0003%.
- Chromium (Cr) improves the oxidation resistance and corrosion resistance at high temperatures of the alloy. When the Cr content is too low, these effects cannot be obtained. On the other hand, when the Cr content is too high, the stability of austenite at high temperatures deteriorates and the creep strength of the alloy decreases. Therefore, the Cr content is 18.0 to 25.0%.
- the lower limit of the Cr content is preferably 18.5%, and more preferably 19.0%.
- the upper limit of the Cr content is preferably 24.5%, and more preferably 24.0%.
- the lower limit of the Ni content is preferably 26.0%, and more preferably 27.0%.
- the upper limit of the Ni content is preferably 37.0%, and more preferably 35.0%.
- Titanium (Ti) combines with Ni to form ⁇ '. Further, Ti combines with C to form TiC, thereby increasing the creep strength and tensile strength of the alloy at high temperatures. When the Ti content is too low, such effects cannot be obtained. On the other hand, when the Ti content is too high, ⁇ ' precipitates excessively, thereby deteriorating the stress relaxation cracking resistance of the alloy. Therefore, the Ti content is 0.10 to 1.60%.
- the lower limit of the Ti content is preferably 0.20%, more preferably 0.30%, and further preferably more than 0.60%.
- the upper limit of the Ti content is preferably 1.50%, more preferably less than 1.50%, and further preferably 1.40%.
- the lower limit of the Al content is preferably 0.08%, and more preferably 0.10%.
- the upper limit of the Al content is preferably 0.90%, and more preferably 0.80%.
- N Nitrogen
- the upper limit of the N content is preferably 0.017%, and more preferably 0.015%.
- the N content is preferably as low as possible. However, excessive reduction thereof will increase production cost. Therefore, the lower limit of the N content is preferably 0.002%, and more preferably 0.004%.
- Oxygen (O) is an impurity. Oxygen deteriorates the hot workability of the alloy, and also deteriorates the toughness and ductility of the alloy. Therefore, the O content is not more than 0.008%.
- the upper limit of the O content is preferably 0.006%, and more preferably 0.005%.
- the O content is preferably as low as possible. However, excessive reduction thereof will increase the production cost. Therefore, the lower limit of the O content is preferably 0.0005%, and more preferably 0.0008%.
- Rare earth metal forms a compound with S, thereby decreasing the content of S which has dissolved into the matrix, and improving the stress relaxation cracking resistance of the alloy. Further, REM improves the hot workability and oxidization resistance of the alloy. When the REM content is too low, these effects cannot be obtained. On the other hand, when the REM content is too high, the hot workability and weldability of the alloy will deteriorate. Therefore, the REM content is 0.001 to 0.100%.
- the lower limit of the REM content is preferably 0.003%, and more preferably 0.005%.
- the upper limit of the REM content is preferably 0.090%, and more preferably 0.080%.
- REM is a generic name of a total of 17 elements of Sc, Y, and lanthanoids, and the REM content refers to a total content of one or more elements of REM. Moreover, REM is generally contained in misch metal. For that reason, REM may be added to molten metal as misch metal, and may be adjusted such that the REM content is within the above described range.
- the balance of the chemical composition of the NiCrFe alloy according to the present invention consists of Fe and impurities.
- impurity means an element which is introduced from ores and scraps as the raw material, or from a production environment, etc., when the NiCrFe alloy is industrially produced, and which is permitted within a range not adversely affecting the NiCrFe alloy of the present embodiment.
- NiCrFe alloy according to the present invention may contain B in place of part of Fe.
- B Boron
- B is an optional element and may not be contained.
- B increases the creep strength of the alloy by causing grain boundary carbides to be finely dispersed. Further, B segregates in grain boundaries to assist the effects of REM.
- the B content is 0 to 0.010%.
- the upper limit of the B content is preferably 0.008%.
- the lower limit of the B content to effectively obtain the aforementioned effects is preferably 0.0001%, and more preferably 0.0005%.
- NiCrFe alloy according to the present invention may contain one or two types selected from the group consisting of Ca and Mg in place of part of Fe. Each of these elements forms a compound with S, thereby assisting the effects of REM.
- Calcium (Ca) is an optional element and may not be contained. When contained, Ca forms a compound with S, thereby assisting the S immobilizing effect of REM. If Ca is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the Ca content is too high, Ca forms oxide, and deteriorates the hot workability of the alloy. Therefore, the Ca content is 0 to 0.010%.
- the upper limit of the Ca content is preferably 0.008%.
- the lower limit of the Ca content to effectively obtain the aforementioned effect is preferably 0.0001%, more preferably 0.0002% and further preferably 0.0003%.
- Magnesium (Mg) is an optional element and may not be contained. When contained, Mg forms a compound with S, thereby assisting the S immobilizing effect of REM. When Mg is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the Mg content is too high, Mg forms oxide, thereby deteriorating the hot workability of the alloy. Therefore, the Mg content is 0 to 0.010%.
- the upper limit of the Mg content is preferably 0.008%.
- the lower limit of the Mg content to effectively obtain the aforementioned effect is preferably 0.0001%, more preferably 0.0002% and further preferably 0.0003%.
- NiCrFe alloy according to the present invention may contain one or more types selected from the group consisting of V, Nb, Ta, and Hf in place of part of Fe. Each of these elements forms carbide and carbonitride, thereby increasing the creep strength of the alloy.
- Vanadium (V) is an optional element and may not be contained. When contained, V forms fine carbide and carbonitride with C and N, thereby increasing the creep strength of the alloy. When V is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the V content is too high, a large amount of carbide and carbonitride will precipitate, thereby deteriorating the creep ductility of the alloy. Therefore, the V content is 0 to 0.5%. The upper limit of the V content is preferably 0.4%. The lower limit of the V content to effectively obtain the aforementioned effect is 0.01%.
- Niobium (Nb) is an optional element and may not be contained. When contained, Nb forms fine carbide and carbonitride with C and N, thereby increasing the creep strength of the alloy. When Nb is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the Nb content is too high, a large amount of carbide and carbonitride will precipitate, thereby deteriorating the creep ductility and toughness of the alloy. Therefore, the Nb content is 0 to 1.0%. The upper limit of the Nb content is preferably 0.4%. The lower limit of the Nb content to effectively obtain the aforementioned effect is 0.01%.
- Tantalum (Ta) is an optional element and may not be contained. When contained, Ta forms fine carbide and carbonitride with C and N, thereby increasing the creep strength of the alloy. When Ta is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the Ta content is too high, a large amount of carbide and carbonitride will precipitate, thereby deteriorating the creep ductility and toughness of the alloy. Therefore, the Ta content is 0 to 1.0%. The upper limit of the Ta content is preferably 0.4%. The lower limit of the Ta content to effectively obtain the aforementioned effect is 0.01%.
- Hafnium (Hf) is an optional element and may not be contained. When contained, Hf forms fine carbide and carbonitride with C and N, thereby increasing the creep strength of the alloy. When Hf is contained in any small amount, the aforementioned effect will be obtained to some degree. However, when the Hf content is too high, a large amount of carbide and carbonitride will precipitate, thereby deteriorating the creep ductility and toughness of the alloy. Therefore, the Hf content is 0 to 1.0%. The upper limit of the Hf content is preferably 0.4%. The lower limit of the Hf content to effectively obtain the aforementioned effect is 0.01%.
- NiCrFe alloy according to the present invention may contain one or more types selected from the group consisting of Mo, W, Co, and Cu in place of part of Fe.
- Molybdenum (Mo) is an optional element and may not be contained. When contained, Mo dissolves into the alloy, thereby increasing the creep strength of the alloy at high temperatures. When Mo is contained in any small amount, such effect will be obtained to some degree. However, when the Mo content is too high, the stability of austenite will be lost, thereby deteriorating the toughness of the alloy. Therefore, the Mo content is 0 to 1.0%. The upper limit of the Mo content is preferably 0.9%. The lower limit to effectively obtain the aforementioned effect is preferably 0.01%.
- Tungsten (W) is an optional element and may not be contained. When contained, W dissolves into the alloy, thereby increasing the creep strength of the alloy at high temperatures. When W is contained in any small amount, such effect will be obtained to some degree. However, when the W content is too high, the stability of austenite will be lost, thereby deteriorating the toughness of the alloy. Therefore, the W content is 0 to 2.0%. The upper limit of the W content is preferably 1.8%. The lower limit of the W content to effectively obtain the aforementioned effect is preferably 0.01%.
- Co Co
- Co is an optional element and may not be contained. When contained, Co stabilizes austenite and dissolves into the alloy, thereby increasing the creep strength of the alloy at high temperatures. When Co is contained in any small amount, such effects will be obtained to some degree. However, when the Co content is too high, the production cost increases. Therefore, the Co content is 0 to 3.0%.
- the upper limit of the Co content is preferably 2.8%.
- the lower limit of the Co content to effectively obtain the aforementioned effects is preferably 0.01%.
- Cupper (Cu) is an optional element and may not be contained.
- Cu stabilizes austenite and suppresses precipitation of brittle phase such as ⁇ phase during use at high temperatures.
- the Cu content is 0 to 3.0%.
- the upper limit of the Cu content is preferably 2.5%, and more preferably less than 2.0%.
- the lower limit of the Cu content to effectively obtain the aforementioned effects is preferably 0.01%.
- NiCrFe alloy according to the present invention further satisfies Formula (1): 0.50 ⁇ Ti + 48 Al / 27 ⁇ 2.20 where, each symbol of element in Formula (1) is substituted by the content (mass%) of the corresponding element.
- fn1 Ti + 48A1/27 is an index to indicate the precipitation amount of ⁇ '.
- fn1 indicates a total amount of Ti when the amount of Al is converted into the amount of Ti.
- fn1 is less than 0.50, a sufficient precipitation amount of ⁇ ' will not be obtained, so that the NiCrFe alloy cannot obtain excellent creep resistance.
- fn1 is more than 2.20, the stress relaxation cracking resistance, creep ductility, and toughness of the alloy will deteriorate due to an excessive precipitation amount of ⁇ '. Therefore, fn1 is 0.50 to 2.20. In this range, an appropriate amount of ⁇ ' is precipitated, and excellent creep resistance is obtained.
- the upper limit of the fn1 is preferably 2.00.
- the lower limit of fn1 is preferably 0.65.
- the above described chemical composition further satisfies Formula (2): 0.40 ⁇ Ti / Ti + 48 Al / 27 ⁇ 0.80 where, each symbol of element in Formula (2) is substituted by the content (mass%) of the corresponding element.
- fn2 Ti/(Ti + 48A1/27) is a ratio of the Ti content with respect to the total content of Al and Ti, the content of Al being converted into the amount of Ti.
- fn2 is less than 0.40, the Ti content is too low with respect to the Al content, and the precipitation amount of ⁇ ' decreases. As a result, the NiCrFe alloy cannot obtain excellent creep strength.
- fn2 is more than 0.80, the Ti content becomes excessive with respect to the Al content so that although fine ⁇ ' precipitates in an early stage of creep, the ⁇ ' changes to coarse and acicular ⁇ phase over time. As a result, the creep strength and toughness of the alloy deteriorate. Therefore, fn2 is 0.40 to 0.80. In this range, ⁇ ' precipitates in an appropriate amount, and will not change to ⁇ phase even when further time passes so that excellent creep strength is obtained.
- the upper limit of fn2 is preferably 0.75.
- the above described chemical composition further satisfies Formula (3): ⁇ REM / A REM ⁇ S / 32 ⁇ 2 / 3 ⁇ O / 16 ⁇ 0 where, each symbol of element in Formula (3) is substituted by the content (mass%) of the corresponding element, and A(REM) is substituted by the atomic weight of each REM.
- fn3 ⁇ [REM/(A(REM))] - S/32 - 2/3•O/16 is an index to indicate the amount of S that segregates in grain boundaries.
- fn3 is a negative value, S segregates in grain boundaries, thereby resulting in grain boundary embrittlement so that the stress relaxation cracking resistance of the alloy deteriorates.
- fn3 is not less than 0, REM immobilizes S as inclusions, thereby decreasing the S content in the matrix. As a result, it is possible to improve the stress relaxation cracking resistance of the alloy. Therefore, fn3 is not less than 0.
- the production method of the present embodiment comprises a process of producing an ingot (steelmaking process), and a process of producing a hot-rolled plate (hot working process).
- a process of producing an ingot steelmaking process
- a process of producing a hot-rolled plate hot working process
- alloys having the above described chemical compositions are melted.
- the melting is performed by using, for example, the high-frequency induction vacuum melting.
- an ingot is produced by an ingot-making method.
- hot working is performed once or multiple times.
- the ingot is heated, and thereafter hot working is performed.
- the hot working refers to, for example, hot forging and hot rolling.
- the hot working may be performed by a well-known method.
- the hot-worked NiCrFe alloy may be subjected to cold working.
- the cold working is, for example, cold rolling.
- the NiCrFe alloy which has been subjected to the above described working, may be subjected to heat treatment.
- the heat treatment temperature is preferably 1050 to 1200°C.
- the NiCrFe alloy is preferably water cooled.
- the NiCrFe alloy may be a bar or an alloy pipe.
- the shape of the product will not be limited.
- it is preferable that hot working by hot extrusion is performed.
- NiCrFe alloy produced by the processes described so far has excellent creep strength and excellent stress relaxation cracking resistance.
- ⁇ ' and ⁇ phase precipitate in a use environment at high temperatures.
- the microstructure of the NiCrFe alloy according to the present invention after being kept at 650°C for 3000 hours contains a total of 2 to 6 mass% of ⁇ ' and ⁇ phase, wherein the number density of ⁇ phase is less than 5/100 ⁇ m 2 .
- the ⁇ ' and ⁇ phase are herein also collectively referred to as "aging precipitates”.
- the precipitation amount of ⁇ ' in the alloy will be decreased.
- the NiCrFe alloy cannot obtain excellent creep strength.
- the precipitation amount of ⁇ ' may excessively increase. In that case, the alloy cannot obtain excellent stress relaxation cracking resistance. Therefore, the total of ⁇ ' and ⁇ phase after aging treatment is 2 to 6 mass%.
- the total of ⁇ ' and ⁇ phase can be measured by the following method.
- the NiCrFe alloy according to the present invention is subjected to aging treatment for keeping the alloy at 650°C for 3000 hours.
- a test specimen of 10 mm ⁇ 5 mm ⁇ 50 mm is sampled from the NiCrFe alloy after the aging treatment.
- the alloy is an alloy plate
- the test specimen is sampled from a middle part of plate thickness of the alloy pipe.
- the test specimen is sampled from a middle part of wall thickness. Note that the weight of the test specimen is measured in advance.
- the sampled test specimen is electrolyzed in a 1% tartaric acid-1% (NH 4 ) 2 SO 4 -water solution to sample the residue from the electrolyte.
- the sampled residue is melted by HCl (1+4)-20% tartaric acid solution of 60°C and the solution is filtered.
- the filtrate is measured by ICP emission spectrometry to determine Ti, Al, and Ni concentrations in the residue. From the determined Ti, Al, and Ni concentrations in the residue, and the weight of the test specimen, Ti, Al, and Ni contents in the ⁇ ' and ⁇ phase of the test specimen are determined.
- the sum of Ti, Al, and Ni contents which have been determined by the method described so far, is defined as a sum of ⁇ ' and ⁇ phase (mass%).
- the NiCrFe alloy according to the present invention is subjected to aging treatment for keeping the alloy at 650°C for 3000 hours and then the number density of ⁇ phase is not less than 5/100 ⁇ m 2 , part of ⁇ ' has changed to ⁇ phase. For that reason, the NiCrFe alloy cannot obtain excellent creep strength. Therefore, the number density of ⁇ phase after aging treatment is less than 5/100 ⁇ m 2 .
- the number density of ⁇ phase can be measured by the following method.
- the NiCrFe alloy according to the present invention is subjected to aging treatment for keeping the alloy at 650°C for 3000 hours.
- Microscopic observation is performed on the NiCrFe alloy after aging treatment.
- a microscopic test specimen is sampled from the NiCrFe alloy after aging treatment.
- the alloy is an alloy plate
- the test specimen is sampled from a middle part of the plate thickness.
- the alloy is an alloy pipe
- the microscopic test specimen is sampled from a middle part of wall thickness of the alloy pipe.
- the sampled microscopic test specimen is subjected to mechanical polishing.
- the surface of the microscopic test specimen after mechanical polishing is electrolytically corroded by 10% oxalic acid.
- the microscopic test specimen after electrolytic corrosion is observed by a scanning electron microscope (SEM) in 5 visual fields, and an SEM image is created for each visual field.
- the observation magnification is 10000 times, and observation field is, for example, 12 ⁇ m ⁇ 9 ⁇ m.
- the ⁇ ' and ⁇ phase differ in their shapes. Specifically, ⁇ ' is observed to be spherical and ⁇ phase be acicular. More specifically, an aspect ratio of ⁇ ' is less than 3, and an aspect ratio of ⁇ phase is not less than 3.
- the term "aspect ratio" means a value obtained by dividing the major axis length by the minor axis length for each aging precipitate.
- aging precipitates ( ⁇ ' and ⁇ phase) are identified from contrast. Further, by image processing, aspect ratios are calculated for the identified aging precipitates. To calculate an aspect ratios, general purpose application software may be used. When a calculated aspect ratio is not less than 3, the aging precipitate is identified to be ⁇ phase.
- the number of identified ⁇ phase is counted to determine a sum of the numbers in all visual fields.
- the number density of ⁇ phase in an observation field of 100 ⁇ m 2 (number/100 ⁇ m 2 ) is determined.
- NiCrFe alloy plate materials were produced. Using thus produced NiCrFe alloy plate materials, the following tests were conducted.
- a test specimen was fabricated from the produced alloy plate material.
- the test specimen was sampled from a central part of thickness of the alloy plate material in parallel with the longitudinal direction (rolling direction).
- the specimen was a round bar test specimen, whose parallel part had a diameter of 6 mm, and which had a gauge length of 30 mm.
- the creep rupture test was conducted. The creep rupture test was performed under a tensile load of 70 MPa in the air atmosphere of 750°C.
- a test specimen whose rupture time was not less than 3000 hours was evaluated as "E" (Excellent), and those whose rupture time was less than 3000 hours as "NA" (Not Acceptable).
- test specimens were fabricated by the above described method.
- the fabricated test specimens were subjected to aging treatment to keep them at 650°C for 3000 hours, and the sum (mass%) of ⁇ ' and ⁇ phase of each test specimen was determined by the above described method. Further, the number density of ⁇ phase (number/100 ⁇ m 2 ) was determined by the above described method.
- a sum of ⁇ ' and ⁇ phase of less than 2 mass% was evaluated as "L" (Less), that of 2 to 6 mass% as "E” (Excellent), and that of more than 6 mass% as "TM” (Too Much). Further, those showed a number density of ⁇ phase of not less than 5/100 ⁇ m 2 were evaluated as " ⁇ ".
- the produced alloy plate material was further subjected to cold working. Specifically, cold rolling was performed on the alloy plate material until its thickness became 12 mm. The reduction of area of this cold rolling was 20%.
- a test specimen was fabricated from this alloy plate material. The test specimen was sampled from a central part of thickness of the alloy plate material in parallel with the longitudinal direction (rolling direction). The specimen was a round bar test specimen, whose parallel part had a diameter of 6 mm, and which had a gauge length of 30 mm. By using the specimen, a stress relaxation cracking test was conducted. The stress relaxation cracking test was conducted such that the test specimen is subjected to tensile strain 10% at a strain rate of 0.05 min -1 and is kept as is for 300 hours in air atmosphere of 650°C. A specimen which did not rupture after being kept for 300 hours was evaluated as "E" (Excellent), and one which ruptured as "NA” (Not Acceptable).
- the present invention can be widely applied to uses for which high creep strength and stress relaxation cracking resistance are demanded.
- the present invention can be suitably used for high temperature members of thermal power generation boilers, petroleum refining and chemical industry plants, or the like.
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KR940014865A (ko) | 1992-12-11 | 1994-07-19 | 에드워드 에이. 스틴 | 고온 저항성 니켈-크롬 합금 |
JPH0813104A (ja) | 1994-06-24 | 1996-01-16 | Sanyo Special Steel Co Ltd | 耐ヒートサイクル性に優れた耐熱合金及び該合金を使用したヒーターチューブ |
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EP1777314B9 (en) * | 2004-06-30 | 2016-05-18 | Nippon Steel & Sumitomo Metal Corporation | RAW PIPE OF Fe-Ni ALLOY AND METHOD FOR PRODUCTION THEREOF |
CN101139676A (zh) * | 2006-09-08 | 2008-03-12 | 上海空间电源研究所 | 一种质子交换膜燃料电池流场板耐蚀合金材料 |
DK2246454T3 (en) * | 2008-02-27 | 2015-10-05 | Nippon Steel & Sumitomo Metal Corp | Opkulningsresistent metal material |
CN101260487B (zh) * | 2008-04-17 | 2010-06-02 | 攀钢集团攀枝花钢铁研究院有限公司 | 由含钛高铬镍合金制得的喷涂材料及其制备方法和用途 |
CN101613833B (zh) * | 2008-06-25 | 2011-09-21 | 宝山钢铁股份有限公司 | 高酸性深井用Ni基合金油套管的制造方法 |
CN102369300B (zh) * | 2009-04-01 | 2013-07-24 | 新日铁住金株式会社 | 高强度Cr-Ni合金无缝管的制造方法 |
CN103620077B (zh) * | 2011-06-24 | 2016-02-03 | 新日铁住金株式会社 | 耐渗碳性金属材料 |
JP5212533B2 (ja) * | 2011-11-15 | 2013-06-19 | 新日鐵住金株式会社 | 継目無オーステナイト系耐熱合金管 |
JP5846076B2 (ja) | 2012-03-28 | 2016-01-20 | 新日鐵住金株式会社 | オーステナイト系耐熱合金 |
DE102014001328B4 (de) * | 2014-02-04 | 2016-04-21 | VDM Metals GmbH | Aushärtende Nickel-Chrom-Eisen-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
CN104946932B (zh) * | 2014-03-25 | 2018-04-20 | 新日铁住金株式会社 | 奥氏体系耐热合金管的制造方法以及利用该制造方法制造的奥氏体系耐热合金管 |
JP6257417B2 (ja) * | 2014-03-31 | 2018-01-10 | 新日鐵住金ステンレス株式会社 | 非磁性遊技球用オーステナイト系ステンレス鋼線材及び鋼線 |
CN104018029B (zh) * | 2014-05-21 | 2016-03-23 | 西安热工研究院有限公司 | 一种含稀土的高铁镍铁基双相合金 |
CA2975304A1 (en) * | 2015-02-06 | 2016-08-11 | Atomic Energy Of Canada Limited / Energie Atomique Du Canada Limitee | Nickel-chromium-iron alloys with improved resistance to stress corrosion cracking in nuclear environments |
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2017
- 2017-10-04 CN CN201780061633.5A patent/CN109790610A/zh active Pending
- 2017-10-04 JP JP2018543927A patent/JP6705508B2/ja active Active
- 2017-10-04 WO PCT/JP2017/036059 patent/WO2018066579A1/ja unknown
- 2017-10-04 EP EP17858416.5A patent/EP3524705B1/en active Active
- 2017-10-04 US US16/339,073 patent/US20190284666A1/en not_active Abandoned
- 2017-10-04 KR KR1020197012721A patent/KR20190065352A/ko not_active Application Discontinuation
- 2017-10-04 CA CA3039043A patent/CA3039043A1/en not_active Abandoned
- 2017-10-04 ES ES17858416T patent/ES2843268T3/es active Active
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WO2018066579A1 (ja) | 2018-04-12 |
US20190284666A1 (en) | 2019-09-19 |
JP6705508B2 (ja) | 2020-06-03 |
KR20190065352A (ko) | 2019-06-11 |
EP3524705A4 (en) | 2020-04-08 |
CA3039043A1 (en) | 2018-04-12 |
JPWO2018066579A1 (ja) | 2019-07-11 |
EP3524705A1 (en) | 2019-08-14 |
ES2843268T3 (es) | 2021-07-16 |
CN109790610A (zh) | 2019-05-21 |
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