EP3438306B1 - Ni-fe-cr alloy - Google Patents
Ni-fe-cr alloy Download PDFInfo
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- EP3438306B1 EP3438306B1 EP16897119.0A EP16897119A EP3438306B1 EP 3438306 B1 EP3438306 B1 EP 3438306B1 EP 16897119 A EP16897119 A EP 16897119A EP 3438306 B1 EP3438306 B1 EP 3438306B1
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- 229910000599 Cr alloy Inorganic materials 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims description 65
- 239000000956 alloy Substances 0.000 claims description 65
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 37
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 description 71
- 230000007797 corrosion Effects 0.000 description 71
- 239000010936 titanium Substances 0.000 description 47
- 239000011651 chromium Substances 0.000 description 31
- 238000001556 precipitation Methods 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 22
- 206010070834 Sensitisation Diseases 0.000 description 21
- 230000008313 sensitization Effects 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- 239000010949 copper Substances 0.000 description 13
- 230000007423 decrease Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000005097 cold rolling Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001192 hot extrusion Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
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- 229910001651 emery Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
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- 238000003303 reheating Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
Definitions
- the present invention relates to a Ni-Fe-Cr alloy.
- Installations such as reheating furnace pipes, in a petroleum refining plant and a petrochemical plant are used under high-temperature environments. In addition, those installations are brought into contact with process fluid including sulfides and/or chlorides. Therefore, a material used for the installations is required to have an excellent corrosion resistance.
- Ni-based alloys or Ni-Fe-Cr alloys having excellent corrosion resistances typically Alloy825 (TM), are used.
- Patent Literature 1 Japanese Patent Application Publication No. 61-227148
- Patent Literature 2 Japanese Patent Application Publication No. 6-240407
- Patent Literature 1 A high-nickel alloy disclosed in Patent Literature 1 consisting of, in mass percent, C: 0.1% or less, Si: 1.0% or less, Mn: 1.5% or less, S: 0.015% or less, Ni: 30.0 to 30.5%, Cr: 19.0 to 25.0%, Cu: 1.0% or less, Al: 0.1 to 1.0%, Ti: 0.05 to 1.0%, and Nb: 0.05 to 1.0%, with the balance being iron and unavoidable impurities, and satisfies conditions of (3Ti + Nb) / S ⁇ 150 and (Ti + Nb) / C ⁇ 15.
- Patent Literature 1 describes that the high-nickel alloy can be thereby given an excellent intergranular corrosion resistance.
- a high-strength clad steel disclosed in Patent Literature 2 has a base-metal composition consisting of, in mass percent, C: 0.03 to 0.12%, Si: 0.5% or less, Mn: 1 to 1.8%, Nb: 0.06% or less, Mo: 0.25% or less, V: 0.06% or less, and Al: 0.01 to 0.06%, with the balance being Fe and unavoidable impurities.
- the high-strength clad steel is a Ni-based alloy having a cladding-material composition consisting of C: 0.05% or less, Si: 0.5% or less, Mn: 1% or less, Cr: 19.5 to 23.5%, Mo: 2.5 to 3.5%, Al: 0.2% or less, Ti: 0.6 to 1.2%, Cu: 1.5 to 3%, and Ni: 38 to 46%, with the balance being Fe and unavoidable impurities.
- Patent Literature 2 describes that the high-strength clad steel can be provided with an excellent corrosion resistance by heating to 900 to 1030°C, then quenched, and tempering at 500 to 630°C.
- JP 2014-040669 discloses a high corrosion-resistant alloy excellent in intergranular corrosion resistance under nitrate-containing atmosphere by discerning limitation of preferred correlation between C content and Si content to intergranular corrosion resistance, and thereby effectively suppressing deposition of an intermetallic compound such as a Cr carbide or a ⁇ phase to a crystal grain boundary.
- a high corrosion-resistant alloy which is excellent in intergranular corrosion resistance and contains C:0.015 mass% or less, Si:0.45 mass% or less, Mn:2.00 mass% or less, P:0.040 mass% or less, S:0.030 mass% or less, Cr: 19.00 to 25.00 mass%, Mo:2.00 to 8.00 mass%, Fe:20.00 to 40.00 mass%, N:0.001 to 0.300 mass%, Cu:0.01 to 3.00 mass% and Al:0.20 mass% or less, and the balance Ni with inevitable impurities, and satisfies the following expression. Si+8 ⁇ C ⁇ 0.51.
- a Ni-based alloy or a Ni-Fe-Cr alloy may be sensitized in a weld heat affected zone when welding is performed.
- the sensitization may likely cause intergranular corrosion. Therefore, a Ni-based alloy or a Ni-Fe-Cr alloy used under the high-temperature environments described above is required to have an excellent intergranular corrosion resistance achieved by inhibiting the sensitization.
- An objective of the present invention is to provide a Ni-Fe-Cr alloy having an excellent intergranular corrosion resistance.
- a Ni-Fe-Cr alloy of the present embodiment has a chemical composition consisting of, in mass percent, C: 0.005 to 0.015%, Si: 0.05 to 0.50%, Mn: 0.05 to 1.5%, P: 0.030% or less, S: 0.020% or less, Cu: 1.0 to 5.0%, Ni: 30.0 to 45.0%, Cr: 18.0 to 30.0%, Mo: 2.0 to 4.5%, Ti: 0.5 to 2.0%, N: 0.001 to 0.015%, and Al: 0 to 0.50%, with the balance being Fe and impurities.
- Ni-Fe-Cr alloy according to the present invention has an excellent intergranular corrosion resistance.
- the present inventors conducted studies about the sensitization and intergranular corrosion resistance of Ni-Fe-Cr alloys. As a result, the present inventors obtained the following findings.
- the amount of dissolved C in an actual Ni-Fe-Cr alloy is a value determined from the contents of C, Ti, and N in a relative way.
- Ti precipitates in the form of Ti nitride, and thus the amount of Ti available for the immobilization of C is determined as follows.
- C real C ⁇ 0.125 Ti + 0.8571 N + k 1 where, k 1 is a constant of the amount of dissolved C.
- an amount of C used in the precipitation of Cr carbide (total precipitation amount of C (C pre )) is as follows, with a solid-solubility limit of C denoted by k 2 (%).
- C pre C ⁇ 0.125 Ti + 0.8571 N + k 1 ⁇ k 2
- the relation between the average grain size d and unit precipitation amount of C (C unit ) is determined as follows.
- the average grain size is d ( ⁇ m)
- the grain boundary area of a grain is determined as k 3 ⁇ d 2 ⁇ m 2 (k 3 is a constant).
- the number of grains per unit volume is k 4 /d 3 (k 4 is a constant)
- the total grain boundary area is determined as follows.
- the average grain size d is in proportion to the unit precipitation amount of C (C unit ). In other words, the smaller the average grain size d, the less the unit precipitation amount of C (C unit ), and as a result, the sensitization is inhibited.
- the present inventors introduced an idea of an index of the intergranular corrosion resistance based on the average grain size d and the amount of C contributing to the precipitation of Cr carbide described above. As a result, the present inventors found that increasing the intergranular corrosion resistance cannot be simply achieved only reducing the average grain size d, and an appropriate average grain size d exists in the relation with the amount of C contributing to the precipitation of Cr carbide.
- FIG. 1 is a graph illustrating the relation between the amount of C contributing the precipitation of Cr carbide (relative amount of dissolved C (C rel )), the average grain size d ( ⁇ m), and the intergranular corrosion resistance.
- the horizontal axis represents the formula of the total precipitation amount of C (C pre ) from which the constants k 1 and k 2 are omitted (the relative amount of dissolved C (C rel ) to be described later).
- FIG. 1 is obtained through Example to be described later.
- those showed excellent intergranular corrosion resistances are plotted as " ⁇ ”
- those showed poor intergranular corrosion resistances are plotted as " ⁇ ".
- the average grain size d needs to be decreased with an increase in the total precipitation amount of C (C pre ).
- the less the total precipitation amount of C (C pre ) the larger the average grain size d can be made.
- the average grain size d needs to be decreased with an increase in the relative amount of dissolved C (C rel ).
- C rel the relative amount of dissolved C
- F1 is an index of the intergranular corrosion resistance.
- the average grain size d is less than F1
- the average grain size d is proper for the relative amount of dissolved C (C rel ).
- the unit precipitation amount of C (C unit ) is reduced sufficiently, which inhibits the sensitization.
- the intergranular corrosion resistance can be increased.
- the average grain size d is not less than F1
- the average grain size d is excessively large for the relative amount of dissolved C (C rel ).
- the unit precipitation amount of C (C unit ) is not reduced sufficiently, which contributes to the sensitization. As a result, the intergranular corrosion resistance is decreased.
- FIG. 2 is a graph illustrating the relation between the average grain size d ( ⁇ m), the subtraction (F1 - d) of d from F1, and the intergranular corrosion resistance.
- FIG. 2 is obtained through Example to be described later, as with FIG. 1 .
- those showed excellent intergranular corrosion resistances are plotted as " ⁇ "
- those showed poor intergranular corrosion resistances are plotted as " ⁇ ”.
- Formula (1) when the average grain size d satisfies Formula (1), namely, when F1 - d makes a positive value, an excellent intergranular corrosion resistance can be provided even when the average grain size d is large.
- the average grain size d does not satisfy Formula (1), namely, when F1 - d makes a negative value, the intergranular corrosion resistance decreases even when the average grain size d is small.
- a Ni-Fe-Cr alloy according to the present embodiment completed based on the above findings has a chemical composition consisting of, in mass percent, C: 0.005 to 0.015%, Si: 0.05 to 0.50%, Mn: 0.05 to 1.5%, P: 0.030% or less, S: 0.020% or less, Cu: 1.0 to 5.0%, Ni: 30.0 to 45.0%, Cr: 18.0 to 30.0%, Mo: 2.0 to 4.5%, Ti: 0.5 to 2.0%, N: 0.001 to 0.015%, and Al: 0 to 0.50%, with the balance being Fe and impurities.
- the above chemical composition may contain Al: 0.05 to 0.50%.
- the chemical composition of the Ni-Fe-Cr alloy according to the present embodiment consisting of the following elements.
- Carbon (C) increases the strength of the alloy.
- C deoxidizes the alloy.
- An excessively low content of C results in failure to provide these effects.
- an excessively high content of C leads to an increase in precipitation of Cr carbides to grain boundaries, resulting in a decrease in the intergranular corrosion resistance. Consequently, the content of C is 0.005 to 0.015%.
- a lower limit of the content of C is preferably 0.008%.
- An upper limit of the content of C is preferably 0.013%, more preferably 0.010%.
- Si deoxidizes the alloy. An excessively low content of Si results in failure to provide this effect. In contrast, an excessively high content of Si makes inclusions likely to be produced. Consequently, the content of Si is 0.05 to 0.50%. A lower limit of the content of Si is preferably 0.15%, more preferably 0.20%. An upper limit of the content of Si is preferably 0.45%, more preferably 0.40%.
- Mn deoxidizes the alloy.
- An excessively low content of Mn results in failure to provide these effects.
- an excessively high content of Mn causes S to combine with Mn to form a sulfide, which becomes nonmetallic inclusions, resulting in a decrease in pitting resistance. Consequently, the content of Mn is 0.05 to 1.5%.
- a lower limit of the content of Mn is preferably 0.15%, more preferably 0.30%.
- An upper limit of the content of Mn is preferably 1.2%, more preferably 1.0%.
- Phosphorus (P) is an impurity. P segregates in grain boundaries in weld solidification, increasing crack susceptibility that occurs due to embrittlement of a heat affected zone. Therefore, the content of P is 0.030% or less. An upper limit of the content of P is preferably 0.025%, more preferably 0.020%. The content of P is preferably as low as possible.
- S Sulfur
- S is an impurity.
- S segregates in grain boundaries in weld solidification, increasing the crack susceptibility that occurs due to embrittlement of a heat affected zone.
- S forms MnS, resulting in a decrease in the pitting resistance. Therefore, the content of S is 0.020% or less.
- An upper limit of the content of S is preferably 0.010%, more preferably 0.005%.
- the content of S is preferably as low as possible.
- Copper (Cu) increases the corrosion resistance of the alloy.
- An excessively low content of Cu results in failure to provide this effect.
- an excessively high content of Cu results in a decrease in the hot workability of the alloy. Therefore, the content of Cu is 1.0 to 5.0%.
- a lower limit of the content of Cu is preferably 1.2%, more preferably 1.5%.
- An upper limit of the content of Cu is preferably 4.0%, more preferably 3.0%.
- Nickel (Ni) increases the pitting resistance of the alloy. An excessively low content of Ni results in failure to provide this effect. In contrast, an excessively high content of Ni leads to saturation of the effect. Therefore, the content of Ni is 30.0 to 45.0%. A lower limit of the content of Ni is preferably 35.0%, more preferably 38.0%. An upper limit of the content of Ni is preferably 44.5%, more preferably 44.0%.
- Chromium (Cr) increases the corrosion resistance of the alloy.
- An excessively low content of Cr results in failure to provide this effect.
- an excessively high content of Cr leads to a decrease in the stability of austenite at high temperature, resulting in a decrease strength of the alloy in the high temperature. Therefore, the content of Cr is 18.0 to 30.0%.
- a lower limit of the content of Cr is preferably 19.0%, more preferably 20.0%.
- An upper limit of the content of Cr is preferably 26.0%, more preferably 24.0%.
- Molybdenum (Mo) increases the corrosion resistance of the alloy.
- An excessively low content of Mo results in failure to provide this effect.
- an excessively high content of Mo causes Laves phases to precipitate in grain boundaries in an alloy having a high content of Cr, resulting in a decrease in the corrosion resistance of the alloy. Therefore, the content of Mo is 2.0 to 4.5%.
- a lower limit of the content of Mo is preferably 2.4%, more preferably 2.8%.
- An upper limit of the content of Mo is preferably 4.0%, more preferably 3.5%.
- Titanium (Ti) forms Ti carbide, inhibiting the sensitization of the alloy.
- An excessively low content of Ti results in failure to provide this effect.
- an excessively high content of Ti results in a decrease in the hot workability of the alloy. Therefore, the content of Ti is 0.5 to 2.0%.
- a lower limit of the content of Ti is preferably 0.55%, more preferably 0.60%.
- An upper limit of the content of Ti is preferably 1.5%, more preferably 1.3%.
- N Nitrogen
- N forms fine carbo-nitrides in grains, increasing the strength, and therefore may be contained.
- an excessively high content of N causes Ti to combine with N to form TiN, which hinders C from being immobilized in the form of Ti carbide, resulting in a decrease in inhibition of sensitization. Therefore, the content of N is 0.001 to 0.015%.
- a lower limit of the content of N is preferably 0.002%, more preferably 0.005%.
- An upper limit of the content of N is preferably 0.013%, more preferably 0.010%.
- the balance of the chemical composition of the Ni-Fe-Cr alloy according to the present embodiment is Fe and impurities.
- the impurities mean elements that are mixed from ores and scraps used as raw material, a producing environment, or the like when the Ni-Fe-Cr alloy is produced in an industrial manner, and are allowed to be mixed within ranges in which the impurities have no adverse effect on the Ni-Fe-Cr alloy according to the present embodiment.
- Ni-Fe-Cr alloy described above may further contain Al in lieu of Fe.
- Aluminum (Al) is an optional element and need not be contained. When contained, Al deoxidizes the alloy. However, an excessively high content of Al results in a decrease in the cleanliness of the alloy and decreases in the workability and ductility of the alloy. Therefore, the content of Al is 0 to 0.50%. A lower limit of the content of Al is preferably 0.05%. An upper limit of the content of Al is preferably 0.30%, more preferably 0.20%. In the present specification, the content of Al means sol.Al (acid-soluble Al).
- F1 is an index of the intergranular corrosion resistance.
- the average grain size d is less than F1
- the average grain size d is proper for the relative amount of dissolved C (C rel ).
- the unit precipitation amount of C (C unit ) is reduced sufficiently, which inhibits the sensitization.
- the intergranular corrosion resistance can be increased.
- the average grain size d is not less than F1
- the average grain size d is excessively large for the relative amount of dissolved C (C rel ).
- the unit precipitation amount of C (C unit ) is not reduced sufficiently, which promotes to the sensitization.
- the intergranular corrosion resistance is decreased.
- the Ni-Fe-Cr alloy according to the present embodiment can be produced by various producing methods. As one example of the producing methods, a producing method for a Ni-Fe-Cr alloy tube will be described below.
- a starting material having the above chemical composition is prepared.
- the starting material is, for example, a hollow billet.
- the hollow billet can be produced by, for example, machining or vertical piercing.
- the hollow billet is subjected to hot extrusion working.
- the hot extrusion working is, for example, the Ugine-Sejournet process.
- a Ni-Fe-Cr alloy pipe is produced.
- the Ni-Fe-Cr alloy tube may be produced by hot working other than the hot extrusion working. The hot working may be repeated several times.
- a cooling rate to reach a temperature of 900°C after final hot working is 0.3°C/sec or higher.
- the cooling rate to reach a temperature of 900°C after the final hot working is 0.3°C/sec or higher, it is possible to adjust the average grain size d such that the average grain size d satisfies Formula (1).
- the Ni-Fe-Cr alloy can have an excellent intergranular corrosion resistance.
- the cooling rate to reach a temperature of 900°C can be made 0.3°C/sec or higher by performing mist cooling after the final hot working.
- cold working including cold rolling and/or cold drawing may be performed.
- Performing the cold working enables the reduction of the average grain size d. In this case, the intergranular corrosion resistance is further increased.
- a final heat treatment such as solution treatment may be performed to obtain a desired mechanical property.
- a lower limit of a heat treatment temperature is preferably 900°C, more preferably 915°C, still more preferably 930°C.
- a lower limit of the heat treatment temperature is preferably 1020°C. In this case, Cr carbide can be dissolved. As a result, the intergranular corrosion resistance can be further inhibited.
- An upper limit of the heat treatment temperature is preferably 1100°C, more preferably 1080°C, still more preferably 1060°C.
- an upper limit of the heat treatment temperature is preferably less than 1000°C.
- a heat treatment temperature less than 1000°C enables the precipitation of TiC.
- the heat treatment temperature less than 1000°C enables the reduction of the average grain size d.
- the sensitization can be further inhibited.
- the intergranular corrosion resistance can be further inhibited.
- the sensitization can be inhibited even when the heat treatment is performed at a high temperature of 1000 to 1100°C.
- a heat treatment duration of the final heat treatment is preferably 2 to 30 minutes.
- the description of the above one example of the producing methods has been made about the producing method of a Ni-Fe-Cr alloy tube.
- the Ni-Fe-Cr alloy may be a plate product, a welded tube, a bar product, or the like.
- the Ni-Fe-Cr alloy is not limited to a particular product shape.
- the Ni-Fe-Cr alloy produced by the above producing method has an excellent intergranular corrosion resistance.
- each of the respective ingots was subjected to hot forging at 1200°C, then subjected to hot rolling at 1200°C at a reduction of area of 50%, and further subjected to cold rolling at a reduction of area of 67% to be produced into a plate product having a thickness of 5 mm, a width of 80 mm, and a length of 650 mm.
- each of the respective ingots was subjected to hot forging at 1200°C to be produced into a plate product having a thickness of 15 mm, a width of 60 mm, and a length of 290 mm.
- the cold rolling was not performed.
- the final heat treatment was performed at heat treatment temperatures and for heat treatment durations shown in Table 2.
- the plate products subjected to the heat treatment were subjected to rapid cooling (water cooling).
- the plate products were cut in a direction perpendicular to a rolling direction, and test specimens having a thickness of 5 mm, a width of 20 mm, and a length of 10 mm were taken.
- the test specimens were each embedded in resin in such a manner that a surface including the rolling direction of the plate product (longitudinal section of the test specimen) becomes an observation surface, and the observation surface was subjected to mirror polish.
- the polished surface was etched using mixed acid.
- the etched observation surface was observed under an optical microscope.
- the average grain size d five visual fields were shot at 100x magnification to determine the average grain size d ( ⁇ m).
- test specimen having a thickness of 5 mm, a width of 10 mm, and a length of 50 mm was taken.
- the lengthwise direction of the test specimen was parallel to the lengthwise direction of the plate product.
- the test specimen was subjected to sensitization heat treatment at 700°C for 60 minutes, which was a simulation of a weld heat affected zone.
- the surface of the test specimen subjected to the sensitization heat treatment was finished by wet emery polishing at #600, degreased with acetone, and dried.
- the test specimen was subjected to the intergranular corrosion test according to the ASTM A262 C method, and the intergranular corrosion resistance of the etched test specimen was evaluated.
- a test bath was a boiled 65% nitric acid, and three batches of an immersion test were performed, the three batches each taking 48 hours. A corrosion loss in each of the batches was measured, and from the corrosion rate in the three batches, the average corrosion rate was calculated.
- Test Number 19 the content of Ti was excessively high. This made the hot workability low, making the working unable, and thus Test Number 19 fell outside the test.
- the cooling rate to reach 900°C after the final hot working was less than 0.3°C/s. Therefore, even with the heat treatment temperature set at less than 1000°C, the average grain size d was large as compared with Test Number 2, being not less than F1. As a result, the intergranular corrosion resistance was low.
- the cooling rate to reach 900°C after the final hot working was less than 0.3°C/s. Therefore, the average grain size d was large as compared with Test Number 3, being not less than F1. As a result, the intergranular corrosion resistance was low.
- the cooling rate to reach 900°C after the final hot working was less than 0.3°C/s.
- the cold rolling was not performed after the hot working. Therefore, even with the heat treatment temperature set at less than 1000°C, the average grain size d was large as compared with Test Number 5, being not less than F1. As a result, the intergranular corrosion resistance was low.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Powder Metallurgy (AREA)
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JP2016070797 | 2016-03-31 | ||
PCT/JP2016/089088 WO2017168904A1 (ja) | 2016-03-31 | 2016-12-28 | Ni-Fe-Cr合金 |
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EP3438306A1 EP3438306A1 (en) | 2019-02-06 |
EP3438306A4 EP3438306A4 (en) | 2019-12-18 |
EP3438306B1 true EP3438306B1 (en) | 2021-02-24 |
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US (1) | US20190100826A1 (ko) |
EP (1) | EP3438306B1 (ko) |
JP (1) | JP6579263B2 (ko) |
KR (1) | KR20180125566A (ko) |
CN (1) | CN109072365A (ko) |
CA (1) | CA3018312C (ko) |
ES (1) | ES2865379T3 (ko) |
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CN108977804A (zh) * | 2018-07-06 | 2018-12-11 | 武汉北方新创环保科技发展有限公司 | 一种锅炉水冷壁复合管及其制备方法 |
JP7332258B2 (ja) * | 2018-12-11 | 2023-08-23 | 山陽特殊製鋼株式会社 | 耐粒界腐食性や耐孔食性に優れ、かつ熱間加工性および冷間加工性に優れた高Niの耐食合金 |
CN110306104B (zh) * | 2019-08-06 | 2021-07-06 | 华北理工大学 | 一种耐腐蚀合金及其制备方法 |
WO2023145895A1 (ja) * | 2022-01-28 | 2023-08-03 | 日本製鉄株式会社 | Ni-Fe-Cr合金溶接継手 |
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ATE33404T1 (de) * | 1983-08-10 | 1988-04-15 | Ver Edelstahlwerke Ag | Nickel-knetlegierung und verfahren zur waermebehandlung derselben. |
JPS6077918A (ja) * | 1983-10-05 | 1985-05-02 | Nippon Kokan Kk <Nkk> | 耐食性合金鋼の製造方法 |
JPH02185943A (ja) * | 1989-01-11 | 1990-07-20 | Nippon Steel Corp | 熱間加工性に優れた油井管及びラインパイプ用高耐食Ti含有合金 |
JPH03120342A (ja) * | 1989-09-30 | 1991-05-22 | Kubota Corp | 鋳造材の熱処理方法 |
FR2698883B1 (fr) * | 1992-12-09 | 1995-01-13 | Sima Sa | Alliage base nickel du système quaternaire Ni-Fe-Cr-Mo à durcissement par précipitation de phase gamma prime et résistant aux modes de corrosion rencontrés notamment dans l'industrie pétrolière. |
JP2001335893A (ja) * | 2000-05-30 | 2001-12-04 | Nippon Steel Corp | 表面性状及び加工性に優れた熱延鋼板及びその製造方法 |
CA2572156C (en) * | 2004-06-30 | 2013-10-29 | Sumitomo Metal Industries, Ltd. | Fe-ni alloy pipe stock and method for manufacturing the same |
CN101760687A (zh) * | 2008-12-10 | 2010-06-30 | 辽阳石化机械设计制造有限公司 | 一种高温合金管件及其所用钢材和管件的生产方法 |
JP5682602B2 (ja) * | 2012-08-09 | 2015-03-11 | 新日鐵住金株式会社 | 内面品質に優れたNi含有高合金丸ビレットの製造方法 |
MY178493A (en) * | 2013-05-09 | 2020-10-14 | Jfe Steel Corp | Nickel-base alloy-clad steel plate having good resistance to intergranular corrosion and producing method thereof |
JP2014040669A (ja) * | 2013-10-10 | 2014-03-06 | Nippon Yakin Kogyo Co Ltd | 耐粒界腐食性に優れた高耐食合金 |
CN103556029A (zh) * | 2013-11-04 | 2014-02-05 | 洛阳双瑞特种装备有限公司 | 一种耐腐蚀耐高压密封用垫片制造方法 |
CN104611640B (zh) * | 2015-03-09 | 2016-08-17 | 西安科技大学 | 一种高硼铁基耐冲刷腐蚀合金及其制备方法 |
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- 2016-12-28 ES ES16897119T patent/ES2865379T3/es active Active
- 2016-12-28 CN CN201680084233.1A patent/CN109072365A/zh active Pending
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CN109072365A (zh) | 2018-12-21 |
US20190100826A1 (en) | 2019-04-04 |
EP3438306A1 (en) | 2019-02-06 |
SG11201807433RA (en) | 2018-09-27 |
WO2017168904A1 (ja) | 2017-10-05 |
JP6579263B2 (ja) | 2019-09-25 |
CA3018312A1 (en) | 2017-10-05 |
KR20180125566A (ko) | 2018-11-23 |
CA3018312C (en) | 2020-03-10 |
ES2865379T3 (es) | 2021-10-15 |
EP3438306A4 (en) | 2019-12-18 |
JPWO2017168904A1 (ja) | 2018-12-27 |
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