EP2678458B1 - Nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit - Google Patents
Nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit Download PDFInfo
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- EP2678458B1 EP2678458B1 EP12720397.4A EP12720397A EP2678458B1 EP 2678458 B1 EP2678458 B1 EP 2678458B1 EP 12720397 A EP12720397 A EP 12720397A EP 2678458 B1 EP2678458 B1 EP 2678458B1
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- -1 Nickel-chromium-iron-aluminum Chemical compound 0.000 title description 5
- 229910000838 Al alloy Inorganic materials 0.000 title description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 97
- 239000000956 alloy Substances 0.000 claims description 97
- 239000010936 titanium Substances 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052735 hafnium Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 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 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- 239000011651 chromium Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 16
- 238000009864 tensile test Methods 0.000 description 16
- 238000005452 bending Methods 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000003892 spreading Methods 0.000 description 9
- 230000007480 spreading Effects 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910018107 Ni—Ca Inorganic materials 0.000 description 1
- 229910018505 Ni—Mg Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 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
- 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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- 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
-
- 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
- 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%
-
- 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
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Definitions
- the invention relates to a nickel-chromium-iron-aluminum alloy having excellent high-temperature corrosion resistance, creep resistance and improved processability.
- Austenitic nickel-chromium-iron-aluminum alloys with different nickel, chromium and aluminum contents have long been used in furnace construction and in the chemical process industry. For this application, a good high temperature corrosion resistance and a good heat resistance / creep resistance is required even at temperatures above 1000 ° C.
- the high temperature corrosion resistance of the alloys listed in Table 1 increases with increasing chromium content. All these alloys form a chromium oxide layer (Cr 2 O 3 ) with an underlying, more or less closed, Al 2 O 3 layer. Small additions of strongly oxygen-affinitive elements such. B. Y or Ce improve the oxidation resistance. The content of chromium is slowly consumed in the course of use in the application area for the formation of the protective layer. Therefore, a higher chromium content increases the life of the material, because a higher content of the protective layer-forming element chromium retards the time at which the Cr content is below the critical limit and forms oxides other than Cr 2 O 3 , eg ferrous and nickel containing oxides are. A further increase in high temperature corrosion resistance can be achieved by adding aluminum and silicon. From a certain minimum content, these elements form a closed layer below the chromium oxide layer and thus reduce the consumption of chromium.
- the heat resistance / creep resistance at the indicated temperatures is u. a. improved by a high carbon content.
- Alloys such as N06025, N06693 or N06603 are known for their excellent corrosion resistance compared to N06600, N06601 or N06690 due to their high aluminum content. Also, alloys such as N06025 or N06603 show excellent hot strength / creep resistance even at temperatures above 1000 ° C due to the high carbon content.
- z. B. by these high aluminum contents the workability, eg. B. formability and weldability, the deterioration is the stronger, the higher the aluminum content is (N06693). The same applies to an increased degree for silicon, which forms low-melting intermetallic phases with nickel. For N06025 could z. B.
- the EP 0 508 058 A1 discloses an austenitic nickel-chromium-iron alloy consisting of (in weight%) C 0.12-0.3%, Cr 23-30%, Fe 8-11%, Al 1.8 2.4% , Y 0.01 - 0.15%, Ti 0.01 - 1.0%, Nb 0.01 - 1.0%, Zr 0.01 - 0.2%, Mg 0.001 - 0.015%, Ca 0.001 - 0.01%, N max. 0.03%, Si max. 0.5%, Mn max. 0.25%, P max. 0.02%, S max. 0.01%, Ni balance including unavoidable melting impurities.
- the EP 0 549 286 discloses a high temperature resistant Ni-Cr alloy including 55-65% Ni, 19-25%, Cr 1-4.5% Al. 0.045 - 0.3% Y, 0.15 - 1% Ti, 0.005 - 0.5% C, 0.1 - 1.5% Si, 0 - 1% Mn and at least 0.005% in total at least one of the elements of Group containing Mg, Ca, Ce, ⁇ 0.5% in total Mg + Ca, ⁇ 1% Ce, 0.0001 - 0.1% B, 0 - 0.5% Zr, 0.0001 - 0.2 % N, 0 - 10% Co, balance iron and impurities.
- a heat-resistant nickel-based alloy comprising ⁇ 0.1% C, 0.01-2% Si, ⁇ 2% Mn, ⁇ 0.005% S, 10-25% Cr, 2.1- ⁇ 4.5% Al, ⁇ 0.055% N, in total 0.001-1% of at least one of the elements B, Zr, Hf, wherein said elements may be present in the following contents: B ⁇ 0.03%, Zr ⁇ 0.2%, Hf ⁇ 0.8 %.
- Mo and W the following formula must be fulfilled: 2 . 5 ⁇ Not a word + W ⁇ 15
- This object is achieved by a nickel-chromium-aluminum-iron alloy, with (in wt .-%) 12 to 28% chromium, 1.8 to 3.0% aluminum, 1.0 to 15% iron, 0, 01 to 0.5% silicon, 0.005 to 0.5% manganese, 0.01 to 0.20% yttrium, 0.02 to 0.60% titanium, 0.01 to 0.2% zirconium, 0.0002 to 0.05% magnesium, 0.0001 to 0.05% calcium, 0.03 to 0.11% carbon, 0.003 to 0.05% nitrogen, 0.0005 to 0.008% boron, 0.0001 - 0.010% oxygen, 0.001 to 0.030% phosphorus, max. 0.010% sulfur, max. 0.5% molybdenum, max.
- tungsten 0.5% tungsten, wherein yttrium may be wholly or partially replaced by 0.001 to 0.2% lanthanum and / or by 0.001 to 0.2% cerium, if necessary, and wherein titanium may be wholly or partially replaced by 0.001 to 0.6%.
- the spreading range for the element chromium is between 12 and 28%, whereby, depending on the application, chromium contents can be given as follows and adjusted depending on the application in the alloy.
- the alloy further contains calcium in amounts between 0.0001 and 0.05%, in particular 0.0005 to 0.02%.
- the alloy further contains phosphorus at levels between 0.001 and 0.030%, especially 0.002 to 0.020%.
- a maximum of 0.1% of vanadium may be contained in the alloy.
- the alloy of the invention is preferably melted open, followed by treatment in a VOD or VLF plant. After casting in blocks or as a continuous casting, the alloy is hot-formed into the desired semi-finished product, with intermediate annealing between 900 ° C and 1270 ° C for 2 h to 70 h, if necessary.
- the surface of the material may optionally (also several times) be removed chemically and / or mechanically in between and / or at the end for cleaning.
- After the end of the hot forming can optionally be a cold forming with degrees of deformation up to 98% in the desired semi-finished mold, possibly with intermediate anneals between 800 ° C and 1250 ° C for 0.1 min to 70 h, possibly under inert gas such.
- the alloy according to the invention can be produced and used well in the product forms strip, sheet metal, rod wire, longitudinally welded tube and seamless tube.
- the alloy according to the invention is preferably intended for use in furnace construction, e.g. used as a muffle for annealing furnaces, oven rolls or carrier racks.
- Another field of application is the use as a pipe in the petrochemical industry or in solar thermal power plants.
- the alloy can be used as a jacket in glow plugs, as a catalyst carrier film and as a component in exhaust systems.
- the alloy according to the invention is well suited for the production of deep drawn parts.
- the deformability is determined in a tensile test according to DIN EN ISO 6892-1 at room temperature.
- the yield strength R p0.2 , the tensile strength R m and the elongation A are determined until the fracture.
- the experiments were carried out on round samples with a diameter of 6 mm in the measuring range and a measuring length L 0 of 30 mm. The sampling took place transversely to the forming direction of the semifinished product.
- the forming speed at R p0.2 was 10 MPA / s and at R m was 6.7 10 -3 1 / s (40% / min).
- the amount of elongation A in the tensile test at room temperature can be taken as a measure of the deformability.
- a good workable material should have an elongation of at least 50%.
- Hot crack susceptibility was assessed with the Modified Varestraint Transvarestraint Test (MVT-Test) at the Federal Institute for Materials Research and Testing (see DVS Merkblatt 1004-2).
- MVT-Test Modified Varestraint Transvarestraint Test
- a TIG seam with a constant feed rate is placed fully mechanized on the top side of a material sample measuring 100 mm x 40 mm x 10 mm. As the arc passes the center of the sample, a defined amount of bending strain is applied to it by bending the sample around a female mold of known radius.
- hot cracks form in a localized test zone on the MVT sample.
- the samples were bent lengthwise to the welding direction (Varestraint).
- Varestraint welding direction
- a die speed of 2 mm / s with a yield energy of 7.5 kJ / cm under argon 5.0 and argon with 3, respectively % Nitrogen performed.
- the hot crack resistance is quantified as follows: the lengths of all solidification and reflow cracks that are visible in a light microscope at 25x magnification on the sample are summed. In the same way, the cracks are determined by ductility dip cracks (DDC).
- the material can then be divided into the categories "hot crack-resistant”, “increasing hot crack tendency” and “hot-crack hazard” as follows.
- Total length solidification and re-melting cracks in mm At bending strain hot crack-proof increasing hot crack tendency hot crack at risk 1 % ⁇ 0 ⁇ 7.5 > 7.5 4% ⁇ 15 ⁇ 30 > 30
- the corrosion resistance at higher temperatures was determined in an oxidation test at 1100 ° C in air, the experiment was interrupted every 96 hours and the mass changes of the samples was determined by the oxidation (net mass change m N ).
- the specific (net) mass change is the mass change related to the surface of the samples. 3 samples were removed from each batch.
- the hot strength is determined in a hot tensile test according to DIN EN ISO 6892-2.
- the yield strength R p0.2 , the tensile strength R m and the elongation A up to the break are determined analogously to the tensile test at room temperature (DIN EN ISO 6892-1).
- the experiments were carried out on round samples with a diameter of 6 mm in the measuring range and an initial measuring length L 0 of 30 mm. The sampling took place transversely to the forming direction of the semifinished product.
- the forming speed at R p0 , 2 was 8.33 10 -5 1 / s (0.5% / min) and at R m was 8.33 10 -4 1 / s (5% / min).
- the sample is installed at room temperature in a tensile testing machine and heated to a desired temperature without load with a tensile force. After reaching the test temperature, the sample is held without load for one hour (600 ° C) or two hours (700 ° C to 1100 ° C) for temperature compensation. Thereafter, the sample is loaded with a tensile force to maintain the desired strain rates, and the test begins.
- Creep resistance is determined by a slow strain rate test (SSRT).
- SSRT slow strain rate test
- a hot tensile test according to DIN EN ISO 6892-2 is carried out with very low forming speeds of 1.0 x 10 -6 1 / s.
- This strain rate is already in the range of creep speeds, so that by means of a comparison of yield strength and in particular tensile strength from a slow tensile test, a ranking of materials in terms of creep resistance can be performed.
- the yield strength R p0.2 , the tensile strength R m and the elongation A to break are determined analogously to the method described for the tensile test at room temperature (DIN EN ISO 6892-1). To reduce the experimental times, the experiments were terminated after about 30% elongation when R m has been reached, otherwise after exceeding the elongation A for R m . The experiments were carried out on round samples with a diameter of about 8 mm in the measuring range and a measuring length L 0 of 40 mm. The sampling took place transversely to the forming direction of the semifinished product.
- the sample is installed at room temperature in a tensile testing machine and heated to a desired temperature without load with a tensile force. After reaching the test temperature, the sample is held without load for two hours (700 ° C to 1100 ° C) for temperature compensation. Thereafter, the sample is loaded with a tensile force to maintain the desired strain rates, and the test begins.
- Tables 2a and 2b show the composition of the alloys studied.
- Alloys N06025 and N06601 are prior art alloys.
- the alloy according to the invention is designated "E”.
- the analyzes of Alloys N06025 and N06601 are in the ranges given in Table 1.
- the alloy "E” according to the invention has a C content which lies in the middle between N06025 and N06601.
- PN and 7.7 C - x • a according to Formulas 2 and 4.
- PN is greater than zero for all alloys in Table 2a. 7.7 C - x • a lies with 0.424 for the alloy according to the invention exactly in the preferred range 0 ⁇ 7.7 C - x • a ⁇ 1.0.
- Table 3 shows the results of the tensile test at room temperature.
- the alloy "E” according to the invention shows, with an elongation of more than 80%, an elongation which is far greater than that of N06025 and N06601. This is not surprising for N06025 because of the high carbon content of 0.17% of the two example batches 163968 and 160483. Both batches show their poorer ductility by an elongation of less than 50%.
- Table 4 shows the results of the MVT tests.
- N06601 is weldable with both argon and argon gases at 3% nitrogen, as all measured total crack lengths are less than 7.5 mm for 1% flexural strain and all measured total crack lengths for 4% flexure are less than 30 mm.
- the measured total crack lengths are greater than 7.5 mm (1% bending strain) or 30 mm (4% bending strain), so that these alloys can not be welded with argon.
- Figure 1 shows the results of the oxidation test at 1100 ° C in air. Plotted is the specific (net) mass change of the samples (average of the 3 samples of each batch) as a function of the removal time.
- the N06601 batch shows a negative specific mass change from the beginning, which is caused by heavy flaking and evaporation of chromium oxide.
- N06025 and the alloy "E” according to the invention initially there is a slight increase in the mass change, followed by a very moderate decrease with time. This shows that both alloys have a low oxidation rate and only a few flaking at 1100 ° C.
- the behavior of the alloy "E” according to the invention, as required, is comparable to that of N06025.
- Table 5 shows the results of the hot tensile tests at 600 ° C, 700 ° C, 800 ° C, 900 ° C and 1100 ° C.
- the highest values for both R p0.2 and R m are expected to be N06025 and the lowest values N06601.
- the values of the alloy "E” according to the invention are in between, the values of the alloy “E” according to the invention being greater than those of N06025 at 800 ° C. for both R p0.2 and R m .
- the strains in the hot tensile tests are sufficiently large for all alloys. At 1100 ° C, no differences between the inventive alloy "E" and N06601 can be determined on account of the measuring accuracy.
- Table 6 shows the results of the slow tensile tests at 700 ° C, 800 ° C and 1100 ° C.
- the highest values for both R p0.2 and R m are , as expected, N06025 and the lowest values N06601.
- the values of alloy "E” according to the invention intervene for R p0.2 , for R m at 700 ° C and 800 ° C they are better or nearly as good as for N06025.
- the elongations in the slow pull tests are sufficient for all alloys large. At 1100 ° C, no differences between the inventive alloy "E" and N06601 can be determined on account of the measuring accuracy.
- R m is comparable to the slow pull tests of N06025 and the invention alloy "E", ie it can be expected that at these temperatures the creep resistance of N06025 and that of the invention alloy “E” is comparable. This shows that for alloys in the preferred range 0 ⁇ 7.7 C - x • a ⁇ 1.0 R m the creep resistance is comparable to that of Nicrofer 6025 HT, while at the same time good processability of the alloy "E" according to the invention in comparison to N06025 ,
- Too low Cr contents mean that the Cr concentration drops very quickly below the critical limit. That's why 12% Cr is the lower limit for chromium. Too high Cr contents deteriorate the workability of the alloy. Therefore, 28% Cr is considered the upper limit.
- Si is needed in the production of the alloy. It is therefore necessary a minimum content of 0.01%. Too high contents in turn affect the processability. The Si content is therefore limited to 0.5%.
- Mn manganese is limited to 0.5% because this element also reduces oxidation resistance.
- additions of oxygen-affine elements improve the oxidation resistance. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries.
- a minimum content of 0.01% Y is necessary to obtain the oxidation resistance-enhancing effect of Y.
- the upper limit is set at 0.20% for cost reasons.
- Y can be replaced in whole or in part by Ce and / or La, since these elements as well as the Y increase the oxidation resistance. Replacement is possible from 0.001%.
- the upper limit is set for cost reasons at 0.20% Ce or 0.20% La.
- Titanium increases the high-temperature strength. At least 0.02% is necessary to achieve an effect. From 0.6%, the oxidation behavior can be worsened.
- Titanium can be wholly or partially replaced by niobium, as niobium also increases high-temperature strength. Replacement is possible from 0,001%. higher Salaries increase costs very much. The upper limit is therefore set at 0.6%.
- Titanium can also be wholly or partially replaced by tantalum, as tantalum also increases high-temperature strength. Replacement is possible from 0,001%. Higher levels increase costs very much. The upper limit is therefore set at 0.6%.
- a minimum content of 0.01% Zr is necessary to obtain the high-temperature strength and oxidation resistance-enhancing effect of Zr.
- the upper limit is set at 0.20% Zr for cost reasons.
- Zr can be wholly or partially replaced by Hf, since this element, such as Zr, also increases high-temperature strength and oxidation resistance. Replacement is possible from 0.001%.
- the upper limit is set at 0.20% Hf for cost reasons.
- Mg manganese-based nickel-semiconductor
- a minimum content of 0.0002% is required.
- Excessively high levels can lead to intermetallic Ni-Mg phases, which significantly impair processability.
- the Mg content is therefore limited to 0.05%.
- a minimum content of 0.03% C is required for good creep resistance.
- C is limited to 0.11% because this element reduces processability.
- N is limited to 0.05% because this element reduces the oxidation resistance.
- the oxygen content must be less than 0.010% to ensure the manufacturability of the alloy. Too small oxygen levels cause increased costs. The oxygen content should therefore be greater than 0.0001%.
- the content of phosphorus should be less than 0.030% since this surfactant affects the oxidation resistance. Too low a P content increases costs. The P content is therefore ⁇ 0.001%.
- the levels of sulfur should be adjusted as low as possible, since this surfactant affects the oxidation resistance. It will therefore max. 0.010% S set.
- Molybdenum is reduced to max. 0.5% limited as this element reduces the oxidation resistance.
- Tungsten is limited to max. 0.5% limited as this element also reduces oxidation resistance.
- 7.7 C - x • a is greater than 1.0, there are so many primary carbides that affect formability. When 7.7 C - x • a is less than 0, heat resistance and creep resistance deteriorate.
- Cobalt can be contained in this alloy up to 5.0%. Higher contents considerably reduce the oxidation resistance. Too low a cobalt content increases the cost. The Co content is therefore ⁇ 0.01%.
- Vanadium is reduced to max. 0.1% limited because this element reduces the oxidation resistance.
- Copper is heated to max. 0.5% limited as this element reduces the oxidation resistance.
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SI201231001T SI2678458T1 (sl) | 2011-02-23 | 2012-02-17 | Nikelj-krom-železo-aluminijeva zlitina z dobro predelovalnostjo |
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DE102012002514.9A DE102012002514B4 (de) | 2011-02-23 | 2012-02-10 | Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit |
PCT/DE2012/000153 WO2012113373A1 (de) | 2011-02-23 | 2012-02-17 | Nickel-chrom-eisen-aluminium-legierung mit guter verarbeitbarkeit |
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US (1) | US9476110B2 (ja) |
EP (1) | EP2678458B1 (ja) |
JP (1) | JP6124804B2 (ja) |
KR (2) | KR20150093258A (ja) |
CN (1) | CN103443312B (ja) |
BR (1) | BR112013021466B1 (ja) |
DE (2) | DE102012013437B3 (ja) |
ES (1) | ES2633014T3 (ja) |
MX (1) | MX347807B (ja) |
RU (1) | RU2568547C2 (ja) |
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DE102012015828B4 (de) * | 2012-08-10 | 2014-09-18 | VDM Metals GmbH | Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit |
CN103409665B (zh) * | 2013-07-02 | 2016-06-01 | 青岛新力通工业有限责任公司 | 铬、镍合金抗高温尘化腐蚀炉管及其离心铸造生产方法 |
RU2533072C1 (ru) * | 2013-10-18 | 2014-11-20 | Сергей Васильевич Афанасьев | Жаропрочный хромоникелевый сплав с аустенитной структурой |
JP2015155790A (ja) * | 2014-01-15 | 2015-08-27 | 日本特殊陶業株式会社 | シースヒータ、グロープラグ |
CN104233137B (zh) * | 2014-08-26 | 2017-05-03 | 盐城市鑫洋电热材料有限公司 | 镍铬合金的变形和热处理工艺 |
CN104347149A (zh) * | 2014-11-03 | 2015-02-11 | 安徽天元电缆有限公司 | 一种铝合金电缆 |
CN104451267A (zh) * | 2014-11-22 | 2015-03-25 | 湘潭高耐合金制造有限公司 | 一种镍钇合金火花塞电极材料及其制备方法 |
CN105349909A (zh) * | 2015-11-20 | 2016-02-24 | 全椒县志宏机电设备设计有限公司 | 一种机械装置用合金材料及其制备方法 |
DE102016111736B4 (de) * | 2016-06-27 | 2020-06-18 | Heraeus Nexensos Gmbh | Hülse zur Abdeckung eines Temperatursensors, Temperaturmessvorrichtung mit einer derartigen Hülse, Verfahren zum Verbinden einer derartigen Hülse mit einer Temperaturmessvorrichtung und Verwendung einer Legierung |
DE102016111738A1 (de) * | 2016-06-27 | 2017-12-28 | Heraeus Sensor Technology Gmbh | Kabel zum Kontaktieren eines Sensors, Temperaturmessvorrichtung, Verfahren zum Verbinden eines Kabels mit einer Temperaturmessvorrichtung und Verwendung einer Legierung zur Herstellung eines Kabels |
DE102018107248A1 (de) | 2018-03-27 | 2019-10-02 | Vdm Metals International Gmbh | Verwendung einer nickel-chrom-eisen-aluminium-legierung |
DE102020132193A1 (de) | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
DE102020132219A1 (de) | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Verwendung einer Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
IT202100000086A1 (it) * | 2021-01-05 | 2022-07-05 | Danieli Off Mecc | Apparato per il riscaldo di prodotti siderurgici |
CN113088761B (zh) * | 2021-02-21 | 2022-08-05 | 江苏汉青特种合金有限公司 | 一种超高强度耐蚀合金及制造方法 |
CN115449670B (zh) * | 2022-09-14 | 2023-10-20 | 浙江大学 | 一种无中温脆性的高强镍基变形高温合金 |
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US4784830A (en) | 1986-07-03 | 1988-11-15 | Inco Alloys International, Inc. | High nickel chromium alloy |
CA1304608C (en) | 1986-07-03 | 1992-07-07 | Inco Alloys International, Inc. | High nickel chromium alloy |
DE4111821C1 (ja) | 1991-04-11 | 1991-11-28 | Vdm Nickel-Technologie Ag, 5980 Werdohl, De | |
DE69202965T2 (de) * | 1991-12-20 | 1996-03-14 | Inco Alloys Ltd | Gegen hohe Temperatur beständige Ni-Cr-Legierung. |
JPH0750168A (ja) | 1993-08-04 | 1995-02-21 | Mitsubishi Materials Corp | 溶融炭酸塩燃料電池のセパレータ材 |
JPH07114928A (ja) | 1993-10-14 | 1995-05-02 | Mitsubishi Materials Corp | すぐれた高温強度を有する溶融炭酸塩燃料電池のセパレータ材 |
DE19524234C1 (de) | 1995-07-04 | 1997-08-28 | Krupp Vdm Gmbh | Knetbare Nickellegierung |
RU2125110C1 (ru) * | 1996-12-17 | 1999-01-20 | Байдуганов Александр Меркурьевич | Жаропрочный сплав |
US6761854B1 (en) | 1998-09-04 | 2004-07-13 | Huntington Alloys Corporation | Advanced high temperature corrosion resistant alloy |
KR100372482B1 (ko) | 1999-06-30 | 2003-02-17 | 스미토모 긴조쿠 고교 가부시키가이샤 | 니켈 베이스 내열합금 |
JP3644532B2 (ja) | 1999-07-27 | 2005-04-27 | 住友金属工業株式会社 | 熱間加工性、溶接性および耐浸炭性に優れたNi基耐熱合金 |
JP3921943B2 (ja) | 2000-12-15 | 2007-05-30 | 住友金属工業株式会社 | Ni基耐熱合金 |
DE60206464T2 (de) | 2001-12-21 | 2006-07-13 | Hitachi Metals, Ltd. | Ni-Legierung mit verbesserter Oxidations- Resistenz, Warmfestigkeit and Warmbearbeitbarkeit |
JP4172011B2 (ja) | 2001-12-21 | 2008-10-29 | 日立金属株式会社 | 耐酸化性、高温強度及び熱間加工性に優れたNi基合金 |
RU2350674C1 (ru) * | 2008-01-18 | 2009-03-27 | Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт конструкционных материалов "Прометей" (ФГУП ЦНИИ КМ "Прометей") | Жаропрочный сплав |
JP4780189B2 (ja) * | 2008-12-25 | 2011-09-28 | 住友金属工業株式会社 | オーステナイト系耐熱合金 |
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- 2012-02-17 RU RU2013142980/02A patent/RU2568547C2/ru active
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JP6124804B2 (ja) | 2017-05-10 |
US9476110B2 (en) | 2016-10-25 |
DE102012002514B4 (de) | 2014-07-24 |
EP2678458A1 (de) | 2014-01-01 |
MX2013009350A (es) | 2014-03-31 |
RU2568547C2 (ru) | 2015-11-20 |
BR112013021466A8 (pt) | 2018-04-03 |
KR20130122661A (ko) | 2013-11-07 |
RU2013142980A (ru) | 2015-04-10 |
DE102012013437B3 (de) | 2014-07-24 |
KR20150093258A (ko) | 2015-08-17 |
CN103443312A (zh) | 2013-12-11 |
BR112013021466A2 (pt) | 2016-11-01 |
US20130323113A1 (en) | 2013-12-05 |
ES2633014T3 (es) | 2017-09-18 |
DE102012002514A1 (de) | 2012-08-23 |
BR112013021466B1 (pt) | 2019-04-30 |
JP2014513200A (ja) | 2014-05-29 |
WO2012113373A1 (de) | 2012-08-30 |
SI2678458T1 (sl) | 2017-08-31 |
CN103443312B (zh) | 2015-07-08 |
MX347807B (es) | 2017-05-15 |
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