EP3102711A1 - Aushärtende nickel-chrom-eisen-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit - Google Patents
Aushärtende nickel-chrom-eisen-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeitInfo
- Publication number
- EP3102711A1 EP3102711A1 EP15704948.7A EP15704948A EP3102711A1 EP 3102711 A1 EP3102711 A1 EP 3102711A1 EP 15704948 A EP15704948 A EP 15704948A EP 3102711 A1 EP3102711 A1 EP 3102711A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- max
- alloy
- content
- alloy according
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 16
- 230000007797 corrosion Effects 0.000 title claims abstract description 16
- -1 nickel-chromium-iron-titanium-aluminium Chemical compound 0.000 title claims abstract description 10
- 229910000838 Al alloy Inorganic materials 0.000 title abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 159
- 239000000956 alloy Substances 0.000 claims abstract description 159
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000011651 chromium Substances 0.000 claims abstract description 84
- 229910052742 iron Inorganic materials 0.000 claims abstract description 56
- 239000010936 titanium Substances 0.000 claims abstract description 47
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010955 niobium Substances 0.000 claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 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 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 230000008859 change Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 20
- 238000000137 annealing Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 12
- 238000007792 addition Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003892 spreading Methods 0.000 description 9
- 230000007480 spreading Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910001347 Stellite Inorganic materials 0.000 description 7
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 7
- 238000005098 hot rolling Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910018107 Ni—Ca Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910018505 Ni—Mg Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000919 ceramic Substances 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
- 238000013461 design Methods 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
-
- 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
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2301/00—Using particular materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2201/00—Metals
- F05C2201/04—Heavy metals
- F05C2201/0403—Refractory metals, e.g. V, W
- F05C2201/0406—Chromium
Definitions
- the invention relates to a nickel-chromium-iron-titanium-aluminum wrought alloy with very good wear resistance, at the same time good creep resistance, good high temperature corrosion resistance and good processability.
- Austenitic, thermosetting nickel-chromium-titanium-aluminum alloys with different nickel, chromium, titanium and aluminum contents have long been used for exhaust valves of engines.
- a good wear resistance, a good heat resistance / creep resistance, a good fatigue strength and a good high-temperature corrosion resistance (especially in exhaust gases) is required.
- DIN EN 10090 specifies austenitic alloys of which nickel alloys 2.4955 and 2.4952 (NiCr20TiAI) have the highest thermal and creep strengths of all alloys specified in this standard.
- Table 1 shows the composition of the nickel alloys mentioned in DIN EN 10090
- Tables 2 to 4 show the tensile strengths, the 0.2% proof stress and creep resistance values after 1000 h.
- NiFe25Cr20NbTi with 0.05-0.10% C, max. 1, 0% Si, max. 1, 0% Mn, max.
- NiCr20TiAI has significantly higher tensile strengths, 0.2% yield strengths and higher creep rupture strength than NiFe25Cr20NbTi.
- EP 0 639 654 A2 discloses an iron nickel-chromium alloy consisting of (in weight%) up to 0.15% C, up to 1.0% Si, up to 3.0% Mn, 30 to 49% Ni, 10 to 18% Cr, 1, 6 to 3.0% Al, one or more elements from the group IVa to Va with a total content of 1.5 to 8.0%, balance Fe and inevitable impurities, wherein AI is an indispensable additional element and one or more elements from the already mentioned group IVa to Va must satisfy the following formula in atom%:
- WO 2008/007190 A2 discloses a wear-resistant alloy consisting of (in% by weight) 0.15 to 0.35% C, up to 1.0% Si, up to 1.0% Mn,> 25 to ⁇ 40 % Ni, 15 to 25% Cr, up to 0.5% Mo, up to 0.5% W,> 1, 6 to 3.5% Al,> 1, 1% to 3% in total Nb plus Ta, up to 0.015% B, remainder Fe and unavoidable impurities, where Mo + 0.5W ⁇ 0.75%; Ti + Nb> 4.5% and 13 ⁇ (Ti + Nb) / C ⁇ 50.
- the alloy is particularly useful for the manufacture of exhaust valves for internal combustion engines.
- the good wear resistance of this alloy is based on the high proportion of primary carbides that form due to the high carbon content. However, a high proportion of primary carbides causes processing problems in the production of this alloy as a wrought alloy.
- the hot strength or creep strength is in the range of 500 ° C to 900 ° C on the additions of aluminum, titanium and / or niobium (or other elements such as Ta, ..) for excretion of y 'and / or ⁇ "phase
- the hot strength or creep resistance also improved by high levels of solid solution strengthening elements such as chromium, aluminum, silicon, molybdenum and tungsten, as well as by a high carbon content.
- alloys with a chromium content around 20% form a chromium oxide layer (Cr 2 O 3 ) protecting the material.
- 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 improves 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, such as ferrous and nickel containing Oxides are.
- the object underlying the invention is to design a nickel-chromium Knet alloy
- This object is achieved by a hardening nickel-chromium-iron-titanium-aluminum wrought alloy with very good wear resistance, at the same time good creep resistance, good high temperature corrosion resistance and good processability with (in mass%)> 18 to 31% chromium, 1, 0 to 3.0% titanium, 0.6 to 2.0% aluminum,> 3.0 to 40% iron , 0.005 to 0.10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, max. 0.010% sulfur, max. 0.020% oxygen, max. 0.70% silicon, max. 2.0% manganese, max. 0.05% magnesium, max. 0.05% calcium, max. 2.0% molybdenum, max. 2.0% tungsten, max.
- the spread range for the chrome element is between> 18 and 31%, whereby preferred ranges can be set as follows:
- the titanium content is between 1, 0 and 3.0%.
- Ti within the spreading range can be adjusted in the alloy as follows: 1.5-3.0%
- the aluminum content is between 0.6 and 2.0%, although here too, depending on the area of use of the alloy, preferred aluminum contents can be set as follows:
- the iron content is between> 3.0 and 40%, whereby, depending on the field of application, preferred contents can be set within the following spreading ranges:
- the alloy contains 0.005 to 0.10% carbon. Preferably, this can be set within the spreading range in the alloy as follows:
- the alloy further contains phosphorus in amounts between 0.0005 and 0.030%.
- Preferred contents can be given as follows:
- the element sulfur is given in the alloy as follows:
- the element oxygen is present in the alloy in a content of max. 0.020% included.
- Preferred further contents can be given as follows:
- the element Si is present in the alloy in levels of max. 0.70% included. Preferred further contents can be given as follows:
- the element Mn in the alloy is in contents of max. 2.0% included. Preferred further contents can be given as follows:
- the element Mg is present in the alloy in a content of max. 0.05% included. Preferred further contents can be given as follows:
- the element Ca is present in the alloy in a content of max. 0.05% included. Preferred further contents can be given as follows:
- the element niobium is in the alloy in contents of max. 0.5% included. Preferred further contents can be given as follows:
- Molybdenum and tungsten are contained singly or in combination in the alloy each containing not more than 2.0%. Preferred further contents can be given as follows:
- a maximum of 0.5% Cu may be contained in the alloy.
- the content of copper may be further limited as follows:
- a maximum of 0.5% vanadium may be present in the alloy.
- the alloy may contain between 0.0 and 15.0% of cobalt as required, which may be further limited as follows:
- the alloy may contain between 0.0 and 0.20% zirconium as required, which may be further limited as follows:
- Preferred areas can be set with
- the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb may be satisfied to provide a sufficiently good processability:
- the element yttrium may be adjusted in levels of 0.0 to 0.20%.
- Y within the spreading range can be set in the alloy as follows:
- the element lanthanum may be adjusted in levels of 0.0 to 0.20%.
- La within the spreading range can be adjusted in the alloy as follows:
- the element Ce may be adjusted in contents of 0.0 to 0.20%.
- Ce can be adjusted within the spreading range in the alloy as follows:
- cerium mischmetal may also be used in amounts of from 0.0 to 0.20%.
- cerium misch metal within the spreading range can be adjusted in the alloy as follows:
- 0.0 to 0.20% hafnium may also be included in the alloy.
- Preferred ranges can be given as follows.
- tantalum may also be included in the alloy
- impurities may still contain the elements lead, zinc and tin in amounts as follows:
- the alloy of the present invention is preferably melted in the vacuum induction furnace (VIM), but may be melted open, followed by treatment in a VOD or VLF plant. After casting in blocks or possibly as a continuous casting, the alloy is optionally annealed at temperatures between 600 ° C and 1 100 ° C for 0, 1 hours (h) to 100 hours, if necessary under inert gas, such. As argon or hydrogen, followed by a cooling in air or in the moving annealing atmosphere. Thereafter, a remelting by means of VAR or ESU, possibly followed by a second remelting process by means of VAR or ESU.
- VIM vacuum induction furnace
- the blocks are optionally annealed at temperatures between 900 ° C and 1270 ° C for 0.1 to 70 hours, then hot formed, optionally with one or more intermediate anneals between 900 ° C and 1270 ° C for 0.05 to 70 hours.
- Hot working can be done, for example, by forging or hot rolling.
- the surface of the material may be chemically (for example several times) in the whole process and / or at the end for cleaning (eg. by pickling) and / or mechanically (eg by machining, by blasting or by grinding).
- the leadership of the thermoforming process can be carried out so that the semi-finished already recrystallized with particle sizes between 5 and 100 pm, preferably between 5 and 40 pm, is present. Possibly.
- inert gas such as. As argon or hydrogen
- a cold forming for example, rolling, drawing, hammering, embossing, pressing
- degrees of deformation up to 98% in the desired semi-finished mold possibly with intermediate annealing between 700 ° C and 1270 ° C for 0, 1 min to 70 hours, if necessary under inert gas, such.
- the final properties of the alloys according to the invention, or the parts produced therefrom, reach through a curing annealing between 600 ° C. and 900 ° C. for 0.1 to 300 hours, followed by an air and / or oven cooling.
- a curing annealing between 600 ° C. and 900 ° C. for 0.1 to 300 hours, followed by an air and / or oven cooling.
- the alloy according to the invention is cured by precipitation of a finely divided ⁇ 'phase.
- two-stage annealing may be performed by first annealing in the range of 800 ° C to 900 ° C for 0.1 to 300 hours, followed by air cooling and / or furnace cooling and 2nd annealing between 600 ° C and 800 ° C for 0.1 to 300 hours followed by air cooling.
- 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. These product forms are having an average grain size of 3 to 600 ⁇ ⁇ ⁇ ⁇ prepared. The preferred range is between 5 ⁇ and 70 ⁇ , in particular between 5 and 40 ⁇ .
- the alloy of the invention can be well by means of forging, upsetting hot extrusion, hot rolling u. ⁇ . process processes. By means of these methods u. a. Manufacture components such as valves, hollow valves or bolts.
- the alloy according to the invention should preferably be used in areas for valves, in particular exhaust valves of internal combustion engines. But also a use in components of gas turbines, as fastening bolts, in springs and in turbochargers is possible.
- the parts produced from the alloy according to the invention in particular z.
- As the valves or the valve seat surfaces can be subjected to further surface treatments such. As a nitration, to further increase the wear resistance.
- the hot strength was determined in a hot tensile test according to DIN EN ISO 6892-2.
- the yield strength R p0 , 2 and the tensile strength R m were determined.
- the experiments were carried out on round samples with a diameter of 6 mm in the measuring range and an initial measuring length of 30 mm. The sampling took place transversely to the forming direction of the semifinished product.
- the forming speed was at R P o, 2 8.33 10 "5 1 / s (0.5% / min) and at R m 8.33 10 '4 1 / s (5% / min).
- the sample was placed in a tensile testing machine at room temperature and heated to the desired temperature with no tensile force. After reaching the test temperature, the sample was held without load for one hour (600 ° C) or two hours (700 ° C to 1 100 ° C) for temperature compensation. Thereafter, the tensile load was applied to the sample to maintain the desired strain rates and testing was begun.
- the creep resistance of a material improves with increasing heat resistance. Therefore, the hot strength is also used to evaluate the creep resistance of the various materials.
- the corrosion resistance at higher temperatures was determined in an oxidation test at 800 ° C in air, the test being interrupted every 96 hours and the mass changes of the samples determined by the oxidation.
- the samples were placed in the ceramic crucible in the experiment, so that possibly spalling oxide was collected and by weighing the crucible containing the oxides, the mass of the chipped oxide can be determined.
- the sum of the mass of the chipped oxide and the mass change of the sample is the gross mass change of the sample.
- the specific mass change is the mass change related to the surface of the samples.
- m ne tto for the specific net mass change
- merutto for the specific gross mass change
- m spa ii for the specific mass change of the chipped oxides.
- the occurring phases in equilibrium were calculated for the different alloy variants with the program JMatPro from Thermotech.
- the database used for the calculations was the TTNI7 nickel base alloy database from Thermotech. This makes it possible to identify phases whose formation in the area of application embrittles the material.
- the temperature ranges can be identified in which z. B. the thermoforming should not take place because it forms phases that strongly solidify the material and thus lead to cracking during thermoforming. For a good processability, especially in the hot forming, such.
- the alloy should have the following properties: • better wear resistance compared to NiCr20TiAI
- the new material is said to have better wear resistance than the reference alloy NiCr20TiAI.
- Stellite 6 was also tested for comparison.
- Stellite 6 is a highly wear-resistant cobalt-based casting alloy with a network of tungsten carbides consisting of approximately 28% Cr, 1% Si, 2% Fe, 6% W, 1, 2% C, but the rest of Co due to its high carbide content must be poured directly into the desired shape. Due to its network of tungsten carbides, Stellite 6 achieves a very high hardness of 438 HV30, which is very advantageous for wear.
- the alloy "E” according to the invention is intended to come as close as possible to the volume loss of Stellite 6. The aim is, in particular, to reduce high-temperature wear between 600 and 800 ° C., which is the relevant temperature range, for example for use as an outlet valve the following criteria apply to the alloys "E” according to the invention:
- Table 3 shows the lower end of the 0.2% yield strength spreading band for NiCr20TiAI when cured at temperatures between 500 and 800 ° C
- Table 2 shows the lower end of the tensile strength spreading band.
- the 0.2% yield strength of the new alloy should be at least in this range for 600 ° C or below 800 ° C this range by not more than 50 MPa to obtain sufficient strength. Ie. In particular, the following values should be achieved:
- the alloy of the invention is said to have a corrosion resistance to air similar to that of NiCr20TiAI. workability
- the heat resistance or creep strength in the range of 500 ° C. to 900 ° C. is based on the addition of aluminum, titanium and / or niobium, which precipitate the ⁇ 'and / or ⁇ . " If the hot forming of these alloys is carried out in the precipitation area of these phases, there is a risk of cracking, ie the hot forming should preferably take place above the solvus temperature ⁇ 5 ⁇ ⁇ (or ⁇ 5 ⁇ ⁇ ) of these phases Hot forming is available, the solvus temperature ⁇ 5 ⁇ '(or ⁇ 5 ⁇ ⁇ ) should be less than 1020 ° C.
- fver ⁇ 7 with (3a) fver 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0, 0109 Fe) Co + 40.67 Ti * Al + 33.28 Al 2 - 13.6 Ti Al 2 - 22.99 Ti - 92.7 Al + 2.94 Nb (3) wherein Cr, Mo, W, Fe , Co, Ti, Al and Nb are the concentration of the elements in mass% and fver in%.
- Tables 5a and 5b show the analyzes of the laboratory scale molten batches together with some used for comparison large scale smelted batches according to the prior art (NiCr20TiAI).
- the batches of the prior art are marked with a T, the inventive with an E.
- the melted laboratory scale batches are marked with an L, the large-scale molten batches with a G.
- Lot 250212 is NiCr20TiAI, but melted as a laboratory batch, and serves for reference.
- the blocks of the laboratory-scale molten alloys in Table 5a and b were annealed between 1100 ° C and 1250 ° C for 0.1 to 70 hours, and by hot rolling and further intermediate annealing between 1100 ° C and 1250 ° C for 0.1 to Hot rolled for 1 hour to a final thickness of 13 mm or 6 mm.
- the temperature control during hot rolling was such that the sheets were recrystallized.
- the large-scale molten comparative batches were melted by VIM and poured into blocks. These blocks were remelted ESU. These blocks were between 1 00 ° C and 1250 ° C for 0.1 min to 70 h, optionally under inert gas, such as. B. argon or hydrogen, followed by cooling in air, annealed in the moving annealing atmosphere or in a water bath and by hot rolling and further intermediate annealing between 1100 ° C and 1250 ° C for 0.1 to 20 hours to a final diameter between 17 and 40 mm hot rolled. The temperature control during hot rolling was such that the sheets were recrystallized. All variants alloy typically had a particle size of 21 to 52 ⁇ ⁇ (see Table 6).
- Table 6 shows Vickers hardness HV30 before and after cure annealing.
- the hardness HV30 in the cured state is in the range of 366 to 416 for all alloys except batch 250330.
- the batch 250330 has a somewhat lower hardness of 346 HV30.
- Table 7 shows the means ⁇ standard deviations of the measurements taken. If the standard deviation is missing, this is a single value.
- the composition of the batches is roughly described in Table 7 in the column Alloy for orientation.
- the maximum values for the volume loss of the alloys according to the invention from the inequalities (4a) for 600 or 800 ° C and (4b) for 25 ° C and 300 ° C entered
- Figure 1 shows the volume loss of the prior art NiCr20TiAI Charge 320776 pin as a function of test temperature measured at 20N, 1 mm sliding path, 20 Hz and with the force measuring module (a).
- the experiments at 25 and 300 ° C were carried out for one hour and the experiments at 600 and 800 ° C were carried out for 10 hours.
- the volume loss decreases strongly with the temperature up to 600 ° C, d. H. the wear resistance noticeably improves at higher temperatures.
- In the high temperature range at 600 and 800 ° C there is a comparatively low volume loss and thus a low wear, which is based on the formation of a so-called “glaze” layer between pin and disc.This "Glaze” layer consists of compacted metal oxides and material of pin and Disc.
- Figure 2 shows the volume loss of the prior art NiCr20TiAI Charge 320776 pen as a function of test temperature measured at 20N, 1 mm sliding path, 20 Hz, and with the force measuring module (s).
- lot 320776 qualitatively the same behavior as with the force modulus (a) shows: the volume loss decreases strongly with temperature up to 600 ° C, whereby the values at 600 and 800 ° C are still smaller than those with the force measuring module ( a) measured.
- the values measured at Steinte 6 are also entered in Fig. 2.
- Figure 4 shows the volume loss of the pen for different laboratory batches compared to NiCr20TiAI, lot 320776 and Steinte 6 at 25 ° C after 1 hour measured at 20 N, glide path 1 mm, 20 Hz with force measuring module (a) and (n).
- the values with force measuring module (s) were systematically smaller than those with force measuring module (a). Taking this into account, it can be seen that NiCr20TiAI as laboratory batch 250212 and as large-scale batch 320776 had a volume loss similar to the measurement accuracy. The laboratory batches can thus be compared directly with the large-scale batches in terms of wear measurements.
- the batch 250325 according to the invention with about 6.5% Fe showed at 25 ° C a volume loss smaller than the maximum value from (4b) for both force measuring modules (see Table 7).
- the volume loss of the 11% Fe charge of the invention 250206 tended to be in the upper spread of lot 320776, but the average was also less than the maximum value of (4a).
- Charge 250327 with 29% Fe according to the invention showed a slightly increased volume loss in the measurements with force measuring module (s), but the mean value here was also smaller than the maximum value from (4b) for both Load modules.
- Co-containing laboratory batches showed a tendency for a reduced volume loss, which at 9.8% Co with force measuring module (s) at 1.04 ⁇ 0.01 mm 3 is just out of the scatter of batch 320776.
- 0.79 ⁇ 0.06 mm 3 showed a significant reduction in volume loss, which then slightly increased again for batch 250330 with the addition of 10% Fe at 0.93 ⁇ 0.02 mm 3 .
- the increase of the Cr content in charge 250326 to 30% compared to the 20% for batch 320776 produced an increase in the volume wear to 1.41 + 0.18 mm 3 (force measuring module (s)), but also below the maximum value of (4a ) was.
- Figure 5 shows the volume loss of the pin for alloys with different carbon contents compared to NiCr20TiAI, lot 320776 at 25 ° C measured at 20 N, glide path 1 mm, 20 Hz with force measuring module (a) after 10 hours. Neither a reduction of carbon content to 0.01% for lot 250211 nor an increase to 0.211% for lot 250214 showed a change in volume loss as compared to lot 320776.
- Figure 6 shows the volume loss of the pin for various alloys compared to NiCr20TiAI, lot 320776 at 300 ° C at 20N, glide path 1mm, 20Hz after 1 hour as measured with force measuring modules (a) and (n).
- the values with force measuring module (s) are systematically smaller than those with force measuring module (a). Taking this into account below, it can be seen that at 300 ° C Steinte 6 was worse than batch 320776.
- the Co-containing laboratory melts 250329 and 250330 showed no reduction in wear volume as at room temperature, but this was in the range of wear volume of NiCr20TiAI, batch 320776 and thus showed no increase as in Stellite 6.
- Figure 7 shows the volume loss of the pin for different alloys compared to NiCr20TiAI, lot 320776 at 600 ° C measured at 20 N, glide path 1 mm, 20 Hz and with force measuring module (a) and (n) after 10 hours.
- the values with force measuring module (s) were systematically smaller than those with force measuring module (a).
- the reference laboratory batch 250212 also had the high temperature range of wear to NiCr20TiAI with 0.066 ⁇ 0.02 mm 3, a similar volume loss, such as the large-scale batch 320776 with 0.053 ⁇ 0.0028 mm 3.
- the laboratory batches can thus be compared with the large-scale batches in terms of wear measurements even in this temperature range.
- Steinte 6 showed a volume loss of 0.009 ⁇ 0.002 mm 3 (force measuring module (s)), which was reduced by a factor of 3. Furthermore, it was found that neither a reduction of the carbon content to 0.01% for batch 25021 nor an increase to 0.21 1% for batch 250214 resulted in a change in the volume loss in comparison to batch 320776 and 250212 (force measuring module (FIG. a)). Also, the addition of 1.4% manganese on Charge 250208 and 4.6% tungsten on Charge 250210 did not result in any significant change in volume loss as compared to Charge 320776 and 250212.
- Figure 8 shows the volume loss of the pin for the different alloys compared to NiCr20TiAI lot 320776 at 800 ° C with 20 N for 2 hours followed by 100 N for 3 hours, all with 1 mm sliding path, 20 Hz measured with force measuring module (s). Also at 800 ° C, it was confirmed that in the high temperature region of wear, the reference laboratory batch 250212 to NiCr20TiAI at 0.292 ⁇ 0.016 mm 3 had a comparable volume loss as the large scale batch 320776 with 0.331 ⁇ 0.081 mm 3 . The laboratory batches could thus be compared directly with the large-scale batches in terms of wear measurements even at 800 ° C.
- the 6.5% iron batch 250325 of the present invention at 0.136 ⁇ 0.025 mm 3 , showed a significant reduction in volume loss as compared to lots 320776 and 250212 below the maximum of 0.156 mm 3 from (4a).
- Lots 250206 with 11% iron of the present invention 0.0557 ⁇ 0.007 mm 3 showed a further reduction in volume loss as compared to the 320776 lot.
- the volume loss was 0.043 ⁇ 0.02 mm 3 . These are both times values well below the maximum value of 0.156 mm 3 from (4a).
- the volume loss of the pin in the wear test could be greatly reduced by an Fe content between> 3 and 40%, so that it at one of the two temperatures 600 and 800 ° C is smaller equal to 50% of the volume loss of NiCr20TiAI (4a).
- the alloys according to the invention with an Fe content of> 3 to 40% also fulfilled the inequalities (4b) at 25 ° C. and 300 ° C.
- the alloys of the invention even had a volume loss reduced by more than 30%.
- An iron content of> 3 to 40% also reduces the metal cost of this alloy.
- Lot 250326 with 30% Cr showed a reduction of the volume loss to 0.042 ⁇ 0.011 mm 3 at 800 ° C and to 0.026 mm 3 both below the respective maximum value at 600 ° C ( Figure 4a).
- the volume loss of 0.2588 mm 3 was also below the maximum value of (4a), as well as at 25 ° C with at 1.41 ⁇ 0.18 mm 3 (force measuring module (s)), so that chromium contents between 18 and 31%, in particular for wear at higher temperatures are beneficial.
- the prior art NiCr20TiAl alloys Batches 320776 and 250212 had a total Cr + Fe + Co of 20.3% and 20.2%, both less than 25%, and met the criteria (4a) and (4b) for a very high Good wear resistance, but especially the criteria (4a) for a good high temperature wear resistance not. Also, lots 250211, 250214, 250208 and 250210, in particular, did not meet the criteria (4a) for good high-temperature wear resistance and had a total Cr + Fe + Co of 20.4%, 20.2%, 20.3% and 20, respectively , 3% all less than 25%.
- the batches 250325, 250206, 250327, 250209, 250329, 250330 and 250326 with Fe and Co additions or an increased Cr content in particular the batches 250325, 250206 and 250327 according to the invention, in any case met the criteria (4a) for 800 ° C, sometimes even additionally for 600 ° C and had a total Cr + Fe + Co of 26.4%, 30.5%, 48.6%, 29.6%, 50.0%, 59.3%, respectively 30.3% all larger 25%. They fulfilled equation (1) for very good wear resistance.
- Table 8 shows the yield strength R p o, 2 and the tensile strength R m for room temperature (RT) for 600X and for 800 ° C.
- RT room temperature
- Table 8 shows the yield strength R p o, 2 and the tensile strength R m for room temperature (RT) for 600X and for 800 ° C.
- the minimum values from inequalities (5a) and (5b) are entered in the last line.
- Figure 10 shows the yield strength R p0 2 and the tensile strength R m for 600 ° C
- Figure 11 for 800 ° C.
- Batches 321863, 321426 and 315828 smelted on an industrial scale had values between 841 and 885 MPa for the yield strength R p0 2 at 600 ° C. and values between 472 and 481 MPa at 800 ° C.
- the reference batch 250212, with a similar analysis as the large-scale batches had a slightly higher aluminum content of 1, 75%, at 600 ° C to a slightly greater yield strength R p0 2 on 866 MPa and 800 ° C of 491 MPa led.
- the laboratory batch 250326 showed that with an addition of 30% Cr, the yield strength R p o, 2 in the tensile test at 800 ° C to 415 MPa decreased, which was still well above the minimum value of 390 MPa. Therefore, an alloy content of 31% Cr is to be regarded as an upper limit for the alloy according to the invention.
- Table 9 shows the specific mass changes after an oxidation test at 800 ° C in air after 6 cycles of 96 h for a total of 576 h. Given in Table 9 are the specific gross mass change, the net specific mass change and the specific mass change of the chipped oxides after 576 h.
- the sample batches of the alloys according to the prior art NiCr20TiAI, batch 321426 and 250212 showed a specific gross mass change of 9.69 or 10.84 g / m 2 and a specific net mass change of 7.81 or 10.54 g / m 2 . Lot 321426 showed minor flakes.
- Batches 250325 (Fe 6.5%), 250206 (Fe 11%) and 250327 (Fe 29%) according to the present invention showed a specific gross mass change of 9.26 to 10.92 g / m 2 and a net mass change of 9.05 to 10.61 g / m 2 , which are in the range of NiCr20TiAI reference alloys and, as required, are not inferior.
- An Fe content of> 3 to 40% does not affect the oxidation resistance negatively.
- Co-containing batches 250209 (Co 9.8%) and 250329 (Co 30%) also had a specific gross mass change of 10.05 and 9.91 g / m 2 and a specific net mass change of 9.81 and 9.81 g / m 2, respectively 9.71 g / m 2 , which were also within the range of the NiCr20TiAI reference alloys and, as required, were no worse than these.
- the batch behaved 250330 (29% Co, 10% Fe) with a specific gross mass change of 9.32 g / m 2 and a specific net change in mass of 8.98 g / m 2.
- a Co content of up to 30% thus does not adversely affect the oxidation resistance.
- Batch 250326 with an increased Cr content of 30% had a specific gross mass change of 6.74 g / m 2 and a specific net change in mass of 6.84 g / m 2, which were below the range of the reference NiCr20TiAI alloys.
- a Cr content of 30% improved the oxidation resistance.
- All of the alloys shown in Table 5b contain Zr, which serves as a reactive element for improving corrosion resistance.
- further reactive elements such as Y, La, Ce, cerium mischmetal, Hf may be added, whose effectiveness is similar to Zr.
- Too low Cr contents mean that when the alloy is used in a corrosive atmosphere, the Cr concentration drops very quickly below the critical limit so that a closed chromium oxide layer can no longer form. Therefore, 18% Cr is the lower limit for chromium. Too high Cr contents increase the soivus temperature T s too much, so that processability deteriorates significantly. That's why 31% is considered the upper limit. Titanium enhances the high temperature strength at temperatures in the range up to 900 ° C by promoting the formation of the ⁇ 'phase. At least 1, 0% is necessary to obtain sufficient strength. Too high titanium contents increase the solvus temperature ⁇ ⁇ ⁇ too much, so that the processability deteriorates significantly. Therefore, 3.0% is considered the upper limit.
- Aluminum increases the high temperature strength at temperatures in the range up to 900 ° C by promoting the formation of the y 'phase. At least 0.6% is necessary to obtain sufficient strength. Too high an aluminum content increases the solvus temperature ⁇ 8 ⁇ ⁇ too much, so that the processability deteriorates significantly. Therefore, 2.0% is considered the upper limit.
- Iron increases wear resistance, especially in the high temperature range. Also, it reduces the cost. In order to obtain a sufficient wear resistance and a sufficient cost reduction, at least> 3.0% is necessary. Excessive iron contents reduce the yield strength too much, especially at 800 ° C. That's why 40% is considered the upper limit.
- Carbon improves creep resistance. A minimum content of 0.005% C is required for good creep resistance. Carbon is limited to a maximum of 0.10%, since this element reduces the processability due to the excessive formation of primary carbides.
- N is limited to a maximum of 0.050%, since this element reduces the processability by the formation of coarse carbonitrides.
- the content of phosphorus should be less than or equal to 0.030%, since this surfactant affects the oxidation resistance. Too low a phosphorus content increases the costs. The phosphorus content is therefore 2.0005%.
- the levels of sulfur should be adjusted as low as possible, since this surfactant affects oxidation resistance and processability. It will therefore max. 0.010% S set.
- the oxygen content must be less than or equal to 0.020% to ensure the manufacturability of the alloy.
- Si content is therefore limited to 0.70%.
- Mg contents and / or Ca contents improve the processing by the setting of sulfur, whereby the occurrence of low-melting NiS Eutektika is avoided. If the contents are too high, intermetallic Ni-Mg phases or Ni-Ca phases may occur, which again significantly impair processability.
- the Mg content or the Ca content is therefore limited to a maximum of 0.05%.
- Molybdenum is reduced to max. 2.0% limited as this element reduces oxidation resistance.
- Tungsten is limited to max. 2.0%, since this element also reduces oxidation resistance and has no measurable positive effect on wear resistance at the carbon contents possible in wrought alloys.
- Niobium increases the high-temperature strength. Higher levels increase costs very much. The upper limit is therefore set at 0.5%. Copper is heated to max. 0.5% limited as this element reduces the oxidation resistance.
- Vanadium is reduced to max. 0.5% limited as this element reduces the oxidation resistance.
- Cobalt increases wear resistance and heat resistance / creep resistance. It may therefore optionally be contained in this alloy between 0 and 15%. Cobalt is an expensive element. Higher levels reduce the cost effectiveness too much.
- the alloy may also contain Zr to improve high temperature strength and oxidation resistance.
- the upper limit is set at 0.20% Zr for cost reasons because Zr is a rare element.
- boron may be added to the alloy because boron improves creep resistance. Therefore, a content of at least 0.0001% should be present. At the same time, this surfactant deteriorates the oxidation resistance. It will therefore max. 0.008% Boron set.
- Nickel stabilizes the austenitic matrix and is required to form the ⁇ 'phase, which is the hot strength / creep resistance. With a nickel content below 35%, the hot strength / creep resistance is reduced too much, which is why 35% is the lower limit.
- the oxidation resistance can be further improved by adding oxygen-affine elements such as yttrium, lanthanum, cerium, hafnium. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries.
- the upper limit of yttrium is set at 0.20% for cost reasons, since yttrium is a rare element.
- the upper limit of lanthanum is set at 0.20% for cost reasons, since lanthanum is a rare element.
- cerium is a rare element.
- cerium mischmetal instead of Ce and or La also cerium mischmetal can be used.
- the upper limit of cerium mischmetal is set at 0.20% for cost reasons.
- the upper limit of hafnium is set at 0.20% for cost reasons, since hafnium is a rare element.
- the alloy may also contain tantalum, since tantalum also increases high-temperature strength by promoting ⁇ 'phase formation. higher Levels increase the cost very much, since tantalum is a rare element. The upper limit is therefore set at 0.60%.
- Pb is set to max. 0.002% limited because this element reduces the oxidation resistance and the high temperature strength. The same applies to Zn and Sn.
- fver ⁇ 7 with (3a) fver 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0, 0109 Fe) Co + 40.67 Ti * Al + 33.28 Al 2 - 13.6 Ti Al 2 - 22.99 Ti - 92.7 Al + 2.94 Nb (3) wherein Cr, Mo, W, Fe , Co, Ti, Al and Nb are the concentration of the elements in mass% and fver in%. The limits for fh were explained in detail in the previous text.
- Table 1 Composition of the nickel alloys for exhaust valves mentioned in DIN EN 10090. All data in mass%,
- Table 2 Reference values for the tensile strength at elevated temperatures of the nickel alloys for exhaust valves mentioned in DIN EN 10090. (+ AT solution annealed: 1000 to 1080 ° C air or water cooling, + precipitation hardened precipitates: 890 to 710/16 h air; 1 ) The values given here are close to the lower scatter band)
- Table 3 Reference values for the 0.2% proof stress at elevated temperatures of the nickel alloys mentioned in DIN EN 10090 for exhaust valves. (+ AT solution annealed: 1000 to 1080 ° C air or water cooling, + precipitation hardened precipitates: 890 to 710/16 h air; 1 ) the values given here are close to the lower scatter band)
- Table 4 Reference values for the creep rupture strength after 1000 hours at elevated temperatures of the nickel alloys for exhaust valves specified in DIN EN 10090 (+ AT Solution annealed: 1000 to 1080 ° C air or water cooling, + P
- Table 5a Composition of large-scale and laboratory batches, Part 1. All concentration data in mass% (T: alloy according to the prior art, E: alloy according to the invention, L: smelted on a laboratory scale, G: melted on an industrial scale)
- Table 6 Results of the particle size determination and the hardness measurement HV30 at room temperature (RT) before (HV30_r) and after (HV30_h) the curing annealing (850 ° C for 4 h / air cooling followed by annealing 700 ° C for 16 h / air cooling); KG grain size.
- T alloy according to the prior art
- E alloy according to the invention
- L melted on a laboratory scale
- G melted on an industrial scale
- Table 7 Wear volume of the pin in mm 3 at a load of 20 N with a sliding path of one mm, a frequency of 20 Hz and a relative humidity of approx. 45% of the large-scale and laboratory batches.
- T alloy according to the prior art
- E alloy according to the invention
- L melted on a laboratory scale
- G melted on an industrial scale
- the mean values ⁇ standard deviation are indicated. If the standard deviation is missing, this is a single value.
- Table 8 Results of tensile tests at room temperature (RT), 600 ° C and 800 ° C.
- the forming speed was R p o, 8.33 10 "5 1 / s (0.5% / min) and R m 8.33 10 ⁇ 1 / s (5% / min);
- KG grain size (T : Alloy according to the prior art, E alloy according to the invention, L: melted on a laboratory scale, G: melted on an industrial scale) * ) Measurement error
- Table 9 Results of the oxidation tests at 800 ° C in air after 576 h. (T: alloy according to the prior art, E alloy according to the invention, L: melted on a laboratory scale, G: melted on an industrial scale)
- Figure 1 Volume loss of the pin made of NiCr20TiAI lot 320776 after the
- Figure 3 Volume loss of the pin made of NiCr20TiAI lot 320776 after the
- Fig. 12 Yield strength R p o, 2 and fh calculated according to formula 2 for the alloys from table 8 at 800 ° C. (L: melted on a laboratory scale, G: melted on an industrial scale).
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Heat Treatment Of Steel (AREA)
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Abstract
Description
Claims
Priority Applications (1)
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SI201530595T SI3102711T1 (sl) | 2014-02-04 | 2015-01-12 | Utrdljiva nikelj-krom-železo-titan-aluminijeva zlitina z dobro obrabno obstojnostjo, obstojnostjo proti lezenju, korozijsko obstojnostjo in obdelovalnostjo |
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DE102014001328.6A DE102014001328B4 (de) | 2014-02-04 | 2014-02-04 | Aushärtende Nickel-Chrom-Eisen-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
PCT/DE2015/000008 WO2015117584A1 (de) | 2014-02-04 | 2015-01-12 | Aushärtende nickel-chrom-eisen-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit |
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EP3102711A1 true EP3102711A1 (de) | 2016-12-14 |
EP3102711B1 EP3102711B1 (de) | 2018-10-31 |
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EP15704948.7A Active EP3102711B1 (de) | 2014-02-04 | 2015-01-12 | Aushärtende nickel-chrom-eisen-titan-aluminium-legierung mit guter verschleissbeständigkeit, kriechfestigkeit, korrosionsbeständigkeit und verarbeitbarkeit |
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US (1) | US20160289807A1 (de) |
EP (1) | EP3102711B1 (de) |
JP (1) | JP6370391B2 (de) |
KR (1) | KR101876399B1 (de) |
CN (1) | CN107041147A (de) |
BR (1) | BR112016011060B1 (de) |
DE (1) | DE102014001328B4 (de) |
SI (1) | SI3102711T1 (de) |
WO (1) | WO2015117584A1 (de) |
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DE102014001330B4 (de) | 2014-02-04 | 2016-05-12 | VDM Metals GmbH | Aushärtende Nickel-Chrom-Kobalt-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
DE102014001329B4 (de) * | 2014-02-04 | 2016-04-28 | VDM Metals GmbH | Verwendung einer aushärtenden Nickel-Chrom-Titan-Aluminium-Legierung mit guter Verschleißbeständigkeit, Kriechfestigkeit, Korrosionsbeständigkeit und Verarbeitbarkeit |
EP3390677B1 (de) * | 2015-12-18 | 2023-01-25 | BorgWarner Inc. | Bypasskomponente, neue legierung enthaltend |
JP6826879B2 (ja) * | 2016-03-23 | 2021-02-10 | 日立金属株式会社 | Ni基超耐熱合金の製造方法 |
EP3524705B1 (de) * | 2016-10-05 | 2020-11-25 | Nippon Steel Corporation | Ni-cr-fe-legierung |
KR102016384B1 (ko) | 2016-10-24 | 2019-08-30 | 다이도 토쿠슈코 카부시키가이샤 | 석출 경화형 고 Ni 내열합금 |
DE102016125123A1 (de) * | 2016-12-21 | 2018-06-21 | Vdm Metals International Gmbh | Verfahren zur Herstellung von Nickel-Legierungen mit optimierter Band-Schweissbarkeit |
KR102344357B1 (ko) | 2017-05-17 | 2021-12-27 | 엘에스전선 주식회사 | 케이블 도체용 알루미늄 합금 |
CN107740804A (zh) * | 2017-10-25 | 2018-02-27 | 苏州华丰不锈钢紧固件有限公司 | 一种高强度耐磨型防腐螺栓 |
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DE102020106433A1 (de) * | 2019-03-18 | 2020-09-24 | Vdm Metals International Gmbh | Nickel-Legierung mit guter Korrosionsbeständigkeit und hoher Zugfestigkeit sowie Verfahren zur Herstellung von Halbzeugen |
DE102020132219A1 (de) * | 2019-12-06 | 2021-06-10 | Vdm Metals International Gmbh | Verwendung einer Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
CN111411265B (zh) * | 2020-03-21 | 2021-11-26 | 交大材料科技(江苏)研究院有限公司 | 一种镍基合金超薄板材 |
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CN114196854B (zh) * | 2020-09-02 | 2022-07-15 | 宝武特种冶金有限公司 | 一种高强度难变形镍基高温合金及其制备方法 |
CN112322940B (zh) * | 2020-11-10 | 2022-04-05 | 中南大学 | 一种高强韧耐腐蚀的富Ni多组分合金及其制备方法 |
CN112593120A (zh) * | 2020-12-09 | 2021-04-02 | 上海蓝铸特种合金材料有限公司 | 一种镍基多元合金及其制成的管材和制备方法 |
CN112813292A (zh) * | 2020-12-25 | 2021-05-18 | 苏州集萃高合材料科技有限公司 | 一种细晶NiCr20TiAl合金锻材的制造方法 |
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 |
CN113088762A (zh) * | 2021-03-31 | 2021-07-09 | 华能国际电力股份有限公司 | 一种高强高韧耐蚀铁镍基高温合金及其制备方法 |
CN116219255A (zh) * | 2021-12-03 | 2023-06-06 | 江苏新华合金有限公司 | 一种新型熔融金属纤维FeCrAlB合金材料及制备方法 |
CN114752817B (zh) * | 2022-04-08 | 2022-09-23 | 南京工程学院 | 一种高温合金模具材料及其制备方法和应用 |
DE102022110383A1 (de) | 2022-04-28 | 2023-11-02 | Vdm Metals International Gmbh | Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in aufkohlenden und sulfidierenden und chlorierenden Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit |
DE102022110384A1 (de) | 2022-04-28 | 2023-11-02 | Vdm Metals International Gmbh | Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in hoch korrosiven Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit |
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JPS50109812A (de) * | 1974-02-09 | 1975-08-29 | ||
JPS58117848A (ja) * | 1982-01-06 | 1983-07-13 | Mitsubishi Metal Corp | 燃焼雰囲気ですぐれた高温耐食性および高温耐酸化性を示す高強度ni基鋳造合金 |
JPS6070155A (ja) * | 1983-09-28 | 1985-04-20 | Hitachi Metals Ltd | 排気弁用Νi基合金 |
JPS60211028A (ja) * | 1984-04-03 | 1985-10-23 | Daido Steel Co Ltd | 排気バルブ用合金 |
JP3132602B2 (ja) * | 1991-09-28 | 2001-02-05 | 大同特殊鋼株式会社 | 摩擦圧接バルブの製造方法 |
DE69202965T2 (de) * | 1991-12-20 | 1996-03-14 | Inco Alloys Ltd | Gegen hohe Temperatur beständige Ni-Cr-Legierung. |
JP3058794B2 (ja) * | 1993-08-19 | 2000-07-04 | 日立金属株式会社 | Fe−Ni−Cr基超耐熱合金、エンジンバルブおよび排ガス触媒用ニットメッシュ |
JPH10219377A (ja) * | 1997-02-07 | 1998-08-18 | Daido Steel Co Ltd | ディーゼルエンジンの高耐食性吸排気バルブ用合金及び吸排気バルブの製造方法 |
JP3952861B2 (ja) * | 2001-06-19 | 2007-08-01 | 住友金属工業株式会社 | 耐メタルダスティング性を有する金属材料 |
JP3951943B2 (ja) * | 2003-03-18 | 2007-08-01 | 本田技研工業株式会社 | 耐過時効特性にすぐれた高強度の排気バルブ用耐熱合金 |
JP4830466B2 (ja) * | 2005-01-19 | 2011-12-07 | 大同特殊鋼株式会社 | 900℃での使用に耐える排気バルブ用耐熱合金およびその合金を用いた排気バルブ |
JP2006274443A (ja) * | 2005-03-03 | 2006-10-12 | Daido Steel Co Ltd | 非磁性高硬度合金 |
US7651575B2 (en) * | 2006-07-07 | 2010-01-26 | Eaton Corporation | Wear resistant high temperature alloy |
DE102007062417B4 (de) * | 2007-12-20 | 2011-07-14 | ThyssenKrupp VDM GmbH, 58791 | Austenitische warmfeste Nickel-Basis-Legierung |
DE102012011162B4 (de) * | 2012-06-05 | 2014-05-22 | Outokumpu Vdm Gmbh | Nickel-Chrom-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
DE102012011161B4 (de) * | 2012-06-05 | 2014-06-18 | Outokumpu Vdm Gmbh | Nickel-Chrom-Aluminium-Legierung mit guter Verarbeitbarkeit, Kriechfestigkeit und Korrosionsbeständigkeit |
-
2014
- 2014-02-04 DE DE102014001328.6A patent/DE102014001328B4/de not_active Expired - Fee Related
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2015
- 2015-01-12 WO PCT/DE2015/000008 patent/WO2015117584A1/de active Application Filing
- 2015-01-12 US US15/037,135 patent/US20160289807A1/en not_active Abandoned
- 2015-01-12 CN CN201580002970.8A patent/CN107041147A/zh active Pending
- 2015-01-12 KR KR1020167021160A patent/KR101876399B1/ko active IP Right Grant
- 2015-01-12 JP JP2016550762A patent/JP6370391B2/ja active Active
- 2015-01-12 EP EP15704948.7A patent/EP3102711B1/de active Active
- 2015-01-12 SI SI201530595T patent/SI3102711T1/sl unknown
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BR112016011060B1 (pt) | 2021-01-26 |
CN107041147A (zh) | 2017-08-11 |
SI3102711T1 (sl) | 2019-03-29 |
JP2017508075A (ja) | 2017-03-23 |
EP3102711B1 (de) | 2018-10-31 |
BR112016011060A2 (pt) | 2017-09-12 |
JP6370391B2 (ja) | 2018-08-08 |
KR20160134647A (ko) | 2016-11-23 |
DE102014001328A1 (de) | 2015-08-06 |
US20160289807A1 (en) | 2016-10-06 |
DE102014001328B4 (de) | 2016-04-21 |
WO2015117584A1 (de) | 2015-08-13 |
KR101876399B1 (ko) | 2018-07-09 |
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