EP2115179B1 - Iron-nickel-chromium- silicon alloy - Google Patents
Iron-nickel-chromium- silicon alloy Download PDFInfo
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- EP2115179B1 EP2115179B1 EP08706757A EP08706757A EP2115179B1 EP 2115179 B1 EP2115179 B1 EP 2115179B1 EP 08706757 A EP08706757 A EP 08706757A EP 08706757 A EP08706757 A EP 08706757A EP 2115179 B1 EP2115179 B1 EP 2115179B1
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- European Patent Office
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- nickel
- alloy
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- 229910000676 Si alloy Inorganic materials 0.000 title abstract description 6
- UIFMYTNHGZJQOH-UHFFFAOYSA-N [Si].[Cr].[Ni].[Fe] Chemical compound [Si].[Cr].[Ni].[Fe] UIFMYTNHGZJQOH-UHFFFAOYSA-N 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000011651 chromium Substances 0.000 claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 118
- 239000000956 alloy Substances 0.000 claims description 118
- 229910052684 Cerium Inorganic materials 0.000 claims description 36
- 238000007665 sagging Methods 0.000 claims description 28
- 238000007792 addition Methods 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052735 hafnium Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 229910001122 Mischmetal Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium 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
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 230000001934 delay 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
- 238000009826 distribution Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
Definitions
- the invention relates to an iron-nickel-chromium-silicon alloy with improved life and dimensional stability.
- Austenitic iron-nickel-chromium-silicon alloys with different nickel, chromium and silicon contents have long been used as heat conductors in the temperature range up to 1100 ° C.
- this alloy group is standardized in DIN 17470 (Table 1) and ASTM B344-83 (Table 2). There are a number of commercially available alloys listed in Table 3 for this standard.
- the lifetime is increased by a higher chromium content, since a higher content of the protective layer forming element chromium Time delays at which the Cr content is below the critical limit and form other oxides than Cr 2 O 3 , which are, for example, iron-containing oxides.
- EP A 0 531 775 discloses a heat-resistant thermoformable austenitic nickel alloy of the following composition (in% by weight): C 0.05-0.15% Si 2.5-3.0% Mn 0.2-0.5% P Max. 0.015% S Max. 0.005% Cr 25-30% Fe 20-27% al 0.05-0.15% Cr 0.001-0.005% SE 0.05-0.15% N 0.05-0.20% Balance Ni and impurities caused by melting.
- the EP-A 0 386 730 describes a nickel-chromium-iron alloy with very good oxidation resistance and high temperature resistance, as desired for advanced heat conductor applications, which emanates from the known NiCr6015 Schuleiterlegmaschine and in which by matching modifications of the composition considerable improvements in performance could be achieved.
- the alloy differs from the known material NiCr6015 in particular in that the rare earth metals are replaced by yttrium, that it additionally contains zirconium and titanium, and that the nitrogen content is specially adapted to the contents of zirconium and titanium.
- an austenitic Fe-Cr-Ni alloy for use in the high-temperature range is to be taken, which has essentially the following chemical composition (in% by weight): Ni 38-48% Cr 18-24% Si 1.0-1.9% C ⁇ 0.1% Fe Rest.
- dislocation creep dislocation creep, grain boundary slippage, or diffusion creep
- dislocation creep does not depend on the grain size.
- the production of a wire with a large grain size increases the creep resistance and thus the dimensional stability.
- grain size should therefore also be taken into account as an important influencing factor.
- Another important factor for a heat conductor material is the highest possible specific electrical resistance and the lowest possible change in the ratio of heat resistance / cold resistance to temperature (temperature coefficient ct).
- iron-nickel-chromium-silicon alloy with (in wt .-%) 34 to 42% nickel, 18 to 26% chromium, 1.0 to 2.5% silicon and additions of 0, 05 to 1% Al, 0.01 to 1% Mn, 0.01 to 0.26% lanthanum, 0.0005 to 0.05% magnesium, 0.01 to 0.14% carbon, 0.01 to 0, 14% nitrogen, max. 0.01% sulfur, max. 0.005% B, balance iron and the usual process-related impurities.
- This alloy due to its special composition, has a longer service life than the alloys of the prior art with the same nickel and chromium contents. In addition, increased dimensional stability or sagging can be achieved than the prior art alloys with 0.04 to 0.10% carbon.
- sulfur and boron may be given in the alloy as follows: sulfur max, 0.01%, preferably max. 0.005% boron Max. 0.005%, preferably max. 0.003%.
- the alloy may further include calcium at levels between 0.0005 and 0.07%, especially 0.001 to 0.05% or 0.01 to 0.05%.
- the alloy may further comprise at least one of the elements Ce, Y, Zr, Hf, Ti with a content of 0.01 to 0, 3%, which can also be defined supplements as needed.
- oxygen-affinity elements such as La, Ce, Y, Zr, Hf, Ti improve the lifetime. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries. The amount of elements available for this mechanism must therefore be normalized to the atomic weight in order to be able to compare the amounts of different elements among each other.
- PwE 200 ⁇ ⁇ X e / Atomic weight of E where E is the relevant element and X E is the content of that element in percent.
- the alloy can have a phosphorus content between 0.001 to 0.020%, in particular from 0.005 to 0.020%.
- impurities may still contain the elements copper, lead, zinc and tin in amounts as follows: Cu Max. 1.0% pb Max. 0.002% Zn Max. 0.002% sn Max. 0.002%.
- the alloy according to the invention is to be used for use in electric heating elements, in particular in electrical heating elements which require high dimensional stability and low sagging.
- a concrete application for the alloy according to the invention is the use in furnace construction.
- Tables 1 to 3 reflect - as already mentioned at the beginning - the state of the art.
- Tables 4a and 4b are industrially molten iron-nickel-chromium-silicon alloys according to the prior art T1 to T7, one on a laboratory scale Prior art molten alloy T8 and a plurality of bench scale inventive experimental alloys V771 to V777, V1070 to V1076, V1090 to V1093 melted to optimize the alloy composition.
- the heat conductor life test is carried out on wires with a diameter of 0.40 mm.
- the wire is clamped between 2 power supply lines at a distance of 150 mm and heated by applying a voltage up to 1150 ° C.
- the heating at 1150 ° C takes place for 2 minutes, then the power supply is interrupted for 15 seconds.
- the burning time is the addition of the "on" times during the life of the wire.
- the relative burning time tb is the indication in% related to the burning time of a reference batch.
- the sagging behavior of heating coils at the application temperature is investigated in a sagging test. This is on heating coils, the sagging of the helices of the Horizontal captured after a certain time. The lower the sag, the greater the dimensional stability or creep resistance of the material.
- T1 and T2 are alloys with about 30% nickel, about 20% Cr and about 2% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE consists of about 60% Ce, about 35% La and the rest Pr and Nd. The relative burning time is 24% or 35%.
- SE rare earth
- the example T3 is an alloy with about 40% nickel, about 20% Cr and about 1.3% Si. It contains rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is 72%.
- SE rare earth
- Examples T4 to T7 are alloys with about 60% nickel, about 16% Cr and about 1.2-1.5% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is in the range of about 100 to 130%.
- SE rare earth
- Tables 4a and 4b contain a number of alloys melted on a laboratory scale.
- the laboratory-scale melted prior art alloy T8 is an alloy of 36.2% nickel, 20.8% Cr, and 1.87% Si.
- T1-T7 Like the industrially produced alloys T1-T7, it contains rare earth (SE) additions in the form of cerium misch metal, which means that SE is and was about 60% Ce, about 35% La and the rest Pr and Nd, apart from the Ni, Cr, and Si contents, melted to the same specifications as the large-scale batches.
- SE rare earth
- the batches according to the prior art T1 to T8 are thus directly comparable.
- the relative burning time of T8 is 53%.
- the Ni content is about 36%, the Cr content about 20% and the Si content about 1.8%.
- the additions to Ce, La, Y, Zr, Hf, Ti, Al, Ca, Mg C, N were varied. These batches can therefore be compared directly with the prior art alloys T8, thus serving as a reference alloy for optimization serves.
- PwE 200 * total X e / Atomic weight of E where E is the element in question and X E is the content of the relevant element in%.
- Fig. 1 shows a graphical representation of the relative burning time tb and the potential PwE for the indicated in the tables 4a and 4b different alloys.
- Range A typical content of active elements
- range B possible content of active elements
- range C too high content of active elements.
- PwE is between 0.11 (T2 and T4) and 0.15 (T6 and T7).
- V1090 and V1072 which did not add cerium mischmetal, ie Ce and La, but Y instead, show a lower relative burn time than T8, although V1090 at 0.10 has a slightly lower PwE but V1072 at 0, 18 has a higher PwE. Y does not appear to work as well as Ce and / or La, so replacement of SE by Y leads to a deterioration over the prior art. Further additions of Zr and Ti (V1074) or Zr and Hf (V1092, V1073, V1091, V1093) in different proportions have succeeded in achieving the service life of T8 again.
- V771 to V777, V1070, V1071 have all been melted with cerium mischmetal, V1075 contains only La.
- the experimental melts V1075 and V777 achieved the highest relative burning time of about 70% of these experimental melts.
- the PwE of V777 is significantly larger at 0.36 than in V1075 at 0.20, which is at the limit of the PwE of the prior art alloys.
- a similar good burning time was achieved with V777 with a combination of 0.06% Ce, 0.02% La, 0.03% Zr and 0.04% Ti.
- V775 with 0.07% Ce and 0.03% La, 0.05% Y and 0.03% Hf with a PwE of 0.30 only has a relative burning time of 46%, indicating that additional doses of Y and Zr to Ce and La are not as effective.
- Figure 2 is a plot of relative burn time and PwE to illustrate the previously described.
- Figure 2 shows the relative burning time of the alloys T1 to T8 according to the prior art as a function of the nickel content.
- the straight lines limit the scattering band in the relative burning time into which the alloys of the prior art fall as a function of the nickel content.
- the trial alloy V1075 with the addition of the best acting element La. Their life is well above the scattering range.
- Table 4b summarizes sagging along with the grain size of the wires.
- the alloys of the prior art T1 to T8 show sagging between 4.5 and 6.2 mm at comparable grain sizes between 20 and 25 microns.
- Figure 3 shows a plot of the nickel content. However, this does not seem to be decisive for sagging.
- Figure 4 shows a plot of the alloys T1 to T8 and the experimental alloys on the C content. Since the experimental alloys have different particle sizes, they were divided into 2 classes: particle sizes from 19 to 26 ⁇ m and particle sizes from 11 to 16 ⁇ m. The alloys T1 to T8 and the trial alloys with a grain size of 19 microns to 26 microns, the comparable Grain sizes all show a similar sagging in the range of 4.5 to 6.2 mm. The experimental alloys, which have a particle size of 11 to 16 microns and a carbon content less than 0.042% have a larger Sagging of about 8 mm, as it is to be expected due to the smaller grain size. The experimental alloys with a grain size of 11 to 16 microns and a carbon content of greater than 0.044% unexpectedly show a lower sagging of 2.8 to 5 mm.
- Figure 5 shows a plot of the alloys T1 to T8 and the experimental melts on the N content.
- Figure 6 shows a plot over the sum C + N. It illustrates once again how C + N significantly reduce sagging.
- a higher C- or N-content thus reduces sagging so much that the sagging-enhancing effect of a smaller grain size is not fully compensated.
- the trial alloys have all been subjected to a standard heat treatment.
- the alloy V777 shows the lowest sagging of all alloys. It has the highest C content and an N content in the upper third. A high C content therefore seems to be particularly effective in reducing sagging.
- Nickel contents below 34% degrade the lifetime (relative burning time), the electrical resistivity and the ct value too much. Therefore, 34% is the lower limit for the nickel content. Too high nickel contents cause higher costs due to the high nickel price. Therefore, 42% should be the upper limit for the nickel content.
- Too low Cr contents mean that the Cr concentration falls too fast below the critical limit. That is why 18% Cr is the lower limit for chromium. Too high Cr contents deteriorate the workability of the alloy. Therefore, 26% Cr is the upper limit.
- a minimum content of 0.01% La is necessary to obtain the oxidation resistance-enhancing effect of La.
- the upper limit is set at 0.26%, which corresponds to a PwE of 0.38. Larger values of PwE are not meaningful as explained in the examples.
- Al is needed to improve the processability of the alloy. It is therefore necessary a minimum content of 0.05%. Too high contents in turn affect the processability.
- the Al content is therefore limited to 1%.
- a minimum content of 0.01% C is necessary for good dimensional stability or low sagging. C is limited to 0.14% because this element reduces oxidation resistance and processability.
- N A minimum content of 0.01% N is necessary for good dimensional stability or low sagging. N is limited to 0.14% because this element reduces oxidation resistance and processability.
- Mg a minimum content of 0.0005% is required as it improves the processability of the material.
- the threshold is set at 0.05%, so as not to soften the positive effect of this element.
- the levels of sulfur and boron should be kept as low as possible, since these surface-active elements affect the oxidation resistance. It will therefore max. 0.01% S and max. 0.005% B is set.
- Copper is heated to max. 1% limited as this element reduces the oxidation resistance.
- Pb is set to max. 0.002% limited because this element reduces the oxidation resistance. The same applies to Sn.
Abstract
Description
Die Erfindung betrifft eine Eisen-Nickel-Chrom-Silizium-Legierung mit verbesserter Lebensdauer und Formstabilität.The invention relates to an iron-nickel-chromium-silicon alloy with improved life and dimensional stability.
Austenitische Eisen-Nickel-Chrom-Silizium-Legierungen mit unterschiedlichen Nickel-, Chrom- und Siliziumgehalten werden seit langen als Heizleiter im Temperaturbereich bis zu 1100°C genutzt. Für die Verwendung als Heizleiterlegierung ist diese Legierungsgruppe in der DIN 17470 (Tabelle 1) und der ASTM B344-83 (Tabelle 2) genormt. Zu dieser Norm gibt es eine Reihe von kommerziell verfügbaren Legierungen, die in Tabelle 3 aufgelistet sind.Austenitic iron-nickel-chromium-silicon alloys with different nickel, chromium and silicon contents have long been used as heat conductors in the temperature range up to 1100 ° C. For use as a heating conductor alloy, this alloy group is standardized in DIN 17470 (Table 1) and ASTM B344-83 (Table 2). There are a number of commercially available alloys listed in Table 3 for this standard.
Der starke Anstieg des Nickelpreises in den letzten Jahren lässt den Wunsch aufkommen, Heizleiterlegierungen mit möglichst niedrigen Nickelgehalten einzusetzen. Dabei entsteht insbesondere der Wunsch die hochnickelhaltigen Varianten NiCr8020, NiCr7030 und NiCr6015 (Tabelle 1), die sich durch besonders vorteilhafte Eigenschaften auszeichnen, durch Materialien mit reduziertem Nickelgehalt zu ersetzen, ohne allzu große Einbußen in der Leistungsfähigkeit der Werkstoffe hinnehmen zu müssen.The sharp increase in the price of nickel in recent years gives rise to the desire to use heat conductor alloys with the lowest possible nickel contents. In particular, there is a desire to replace the high-nickel NiCr8020, NiCr7030 and NiCr6015 (Table 1), which are characterized by particularly advantageous properties, with materials with a reduced nickel content, without having to accept large losses in the performance of the materials.
Generell ist zu bemerken, dass die Lebensdauer und die Einsatztemperatur der in den Tabellen 1 und 2 angegebenen Legierungen mit zunehmendem Nickelgehalt steigen. Alle diese Legierungen bilden eine Chromoxidschicht (Cr2O3), mit einer darunter liegenden, mehr oder weniger geschlossenen, SiO2-Schicht. Geringe Zugaben von stark Sauerstoff affinen Elementen wie Ce, Zr, Th, Ca, Ta (Pfeifer/ Thomas, Zunderfeste Legierungen 2. Auflage, Springer Verlag 1963, Seiten 258 und 259) erhöhen die Lebensdauer, wobei in dem zitierten Fall lediglich der Einfluss eines einzelnen Sauerstoff affinen Elementes untersucht, aber keine Angaben über die Wirkung einer Kombination derartiger Elemente gemacht wurden. Der Chromgehalt wird im Verlauf des Einsatzes eines Heizleiters zum Aufbau der schützenden Schicht langsam verbraucht. Deshalb wird durch einen höheren Chromgehalt die Lebensdauer erhöht, da ein höherer Gehalt des die Schutzschicht bildenden Elementes Chrom den Zeitpunkt hinauszögert, an dem der Cr-Gehalt unter der kritischen Grenze ist und sich andere Oxide als Cr2O3 bilden, was z.B. eisenhaltige Oxide sind.In general, it should be noted that the service life and service temperature of the alloys indicated in Tables 1 and 2 increase with increasing nickel content. All these alloys form a chromium oxide layer (Cr 2 O 3 ), with an underlying, more or less closed, SiO 2 layer. Small additions of strongly oxygen affine elements such as Ce, Zr, Th, Ca, Ta (Pfeifer / Thomas, Zunderfeste alloys 2nd edition, Springer Verlag 1963, pages 258 and 259) increase the life, in the cited case, only the influence of a investigated individual oxygen affinity element, but no information on the effect of a combination of such elements were made. The chromium content is slowly consumed in the course of using a heat conductor to build up the protective layer. Therefore, the lifetime is increased by a higher chromium content, since a higher content of the protective layer forming element chromium Time delays at which the Cr content is below the critical limit and form other oxides than Cr 2 O 3 , which are, for example, iron-containing oxides.
Durch die EP=A 0 531 775 ist eine hitzebeständige warm verformbare austenitische Nickel-Legierung folgender Zusammensetzung (in Gew.-%) bekannt geworden:
In der
Der
Bei freihängenden Heizelementen besteht neben der Forderung nach einer hohen Lebensdauer auch die Forderung nach einer guten Formstabilität bei der Anwendungstemperatur. Ein zu starkes Absacken der Wendel (Sagging) während des Betriebes hat einen ungleichmäßigen Abstand der Windungen mit einer ungleichmäßigen Temperaturverteilung zur Folge, wodurch die Lebensdauer verkürzt wird. Um dies auszugleichen wären mehr Unterstützungspunkte für die Heizwendel erforderlich, was die Kosten erhöht. Das heißt, dass das Heizleitermaterial eine ausreichend gute Formstabilität bzw. Kriechbeständigkeit haben muss.In free-hanging heating elements in addition to the demand for a long life and the requirement for good dimensional stability at the application temperature. Too much sagging during operation results in uneven spacing of the turns with uneven temperature distribution, thereby shortening the life. To compensate this would require more support points for the heating coil, which increases the cost. This means that the heating conductor material must have a sufficiently good dimensional stability or creep resistance.
Die im Bereich der Anwendungstemperatur die Formstabilität beeinträchtigenden Kriechmechanismen (Versetzungskriechen, Korngrenzengleiten oder Diffusionskriechen) werden alle bis auf das Versetzungskriechen durch eine große Korngröße in Richtung größerer Kriechbeständigkeit beeinflusst. Das Versetzungskriechen hängt nicht von der Korngröße ab. Die Erzeugung eines Drahtes mit großer Korngröße erhöht die Kriechbeständigkeit und damit die Formstabilität. Bei allen Betrachtungen sollte deshalb auch die Korngröße als wichtiger Einflussfaktor mit berücksichtigt werden.The creeping mechanisms affecting dislocation stability (dislocation creep, grain boundary slippage, or diffusion creep) are all affected by creep in the direction of greater creep resistance, except for dislocation creep. The dislocation creep does not depend on the grain size. The production of a wire with a large grain size increases the creep resistance and thus the dimensional stability. For all considerations, grain size should therefore also be taken into account as an important influencing factor.
Weiterhin wichtig für ein Heizleitermaterial ist ein möglichst hoher spezifischer elektrischer Widerstand und eine möglichst geringe Änderung des Verhältnisses Warmwiderstand/Kaltwiderstand mit der Temperatur (Temperaturkoeffizient ct).Another important factor for a heat conductor material is the highest possible specific electrical resistance and the lowest possible change in the ratio of heat resistance / cold resistance to temperature (temperature coefficient ct).
Die Varianten mit niedrigerem Nickelgehalt NiCr3020 oder 35Ni, 20Cr (Tabelle 1 bzw. Tabelle 2), die sich durch deutlich geringere Kosten auszeichnen, erfüllen insbesondere die Anforderungen an die Lebensdauer nur unzureichend.The variants with lower nickel content NiCr3020 or 35Ni, 20Cr (Table 1 and Table 2), which are characterized by significantly lower costs, meet in particular the requirements of the life only inadequate.
Die Aufgabe besteht also darin, eine Legierung zu konzipieren, die bei deutlich geringerem Nickelgehalt als NiCr6015 und damit erheblich geringeren Kosten
- a) eine hohe Oxidationsbeständigkeit und eine damit einhergehende hohe Lebensdauer
- b) eine ausreichend gute Formstabilität bei der Anwendungstemperatur
- c) einen hohen spezifischen elektrischen Widerstand in Verbindung mit einer möglichst geringen Änderung des Verhältnisses Warmwiderstand/Kaltwiderstand mit der Temperatur (Temperaturkoeffizient ct) hat.
- a) a high oxidation resistance and a concomitant long life
- b) a sufficiently good dimensional stability at the application temperature
- c) has a high electrical resistivity in conjunction with the smallest possible change in the ratio of heat resistance / cold resistance with the temperature (temperature coefficient ct).
Diese Aufgabe wird gelöst durch eine Eisen-Nickel-Chrom-Silizium-Legierung, mit (in Gew.-%) 34 bis 42 % Nickel, 18 bis 26 % Chrom, 1,0 bis 2,5 % Silizium und Zugaben von 0,05 bis 1 % Al, 0,01 bis 1 % Mn, 0,01 bis 0,26 % Lanthan, 0,0005 bis 0,05 % Magnesium, 0,01 bis 0,14 % Kohlenstoff, 0,01 bis 0,14 % Stickstoff, max. 0,01 % Schwefel, max. 0,005 % B, Rest Eisen und den üblichen verfahrensbedingten Verunreinigungen.This object is achieved by an iron-nickel-chromium-silicon alloy, with (in wt .-%) 34 to 42% nickel, 18 to 26% chromium, 1.0 to 2.5% silicon and additions of 0, 05 to 1% Al, 0.01 to 1% Mn, 0.01 to 0.26% lanthanum, 0.0005 to 0.05% magnesium, 0.01 to 0.14% carbon, 0.01 to 0, 14% nitrogen, max. 0.01% sulfur, max. 0.005% B, balance iron and the usual process-related impurities.
Vorteilhafte Weiterbildungen des Erfindungsgegenstandes sind den zugehörigen Unteransprüchen zu entnehmen.Advantageous developments of the subject invention can be found in the associated dependent claims.
Diese Legierung hat durch ihre besondere Zusammensetzung eine höhere Lebensdauer als die Legierungen nach dem Stand der Technik mit den gleichen Nickel- und Chromgehalten. Zusätzlich lässt sich eine erhöhte Formstabilität bzw. ein geringeres Sagging als die Legierungen nach dem Stand der Technik mit 0,04 bis 0,10 % Kohlenstoff erreichen.This alloy, due to its special composition, has a longer service life than the alloys of the prior art with the same nickel and chromium contents. In addition, increased dimensional stability or sagging can be achieved than the prior art alloys with 0.04 to 0.10% carbon.
Der Spreizungsbereich für das Element Nickel liegt zwischen 34 und 42 %, wobei in Abhängigkeit vom Einsatzfall Nickelgehalte wie folgt gegeben sein können:
- 34-39%
- 34-38%
- 34-37%
- 37-38%.
- 34-39%
- 34-38%
- 34-37%
- 37-38%.
Der Chromgehalt liegt zwischen 18 und 26%, wobei auch hier, je nach Einsatzbereich der Legierung, Chromgehalte wie folgt gegeben sein können:
- 20-24%
- 21-24%.
- 20-24%
- 21-24%.
Der Siliziumgehalt liegt zwischen 1,0 und 2,5 %, wobei, abhängig vom Anwendungsbereich, definierte Gehalte innerhalb des Spreizungsbereiches eingestellt werden können:
- 1,5-2,5%
- 1,0-1,5%
- 1,5-2.0%
- 1,7-2,5%
- 1,2-1,7%
- 1,7-2,2%
- 2,0-2,5%.
- 1.5-2.5%
- 1.0-1.5%
- 1,5-2.0%
- 1.7-2.5%
- 1.2-1.7%
- 1.7-2.2%
- 2.0-2.5%.
Das Element Aluminium ist als Zugabe vorgesehen und zwar in Gehalten von 0,05 bis 1 %. Bevorzugt kann es auch wie folgt in der Legierung eingestellt werden:
- 0,1-0,7%.
- 0.1-0.7%.
Gleiches gilt für das Element Mangan, das mit 0,01 bis 1 % der Legierung zugegeben wird. Alternativ ist auch folgender Spreizungsbereich denkbar:
- 0,1-0,7%.
- 0.1-0.7%.
Der Erfindungsgegenstand geht bevorzugt davon aus, dass sich die in den Beispielen angegebenen Werkstoffeigenschaften im Wesentlichen mit der Zugabe des Elements Lanthan in Gehalten von 0,01 bis 0,26 % einstellen. Je nach Anwendungsbereich können auch hier definierte Werte in der Legierung eingestellt werden:
- 0,01-0,2%
- 0,02-0,15%
- 0,04-0,15%.
- 0.01-0.2%
- 0.02-0.15%
- 0.04-0.15%.
Dies gilt in gleicher Weise für das Element Stickstoff, das in Gehalten zwischen 0,01 und 0,14 % zugegeben wird. Definierte Gehalte können wie folgt gegeben sein:
- 0,02-0,10%
- 0,03-0,09%.
- 0.02-0.10%
- 0.03-0.09%.
Kohlenstoff wird der Legierung in gleicher Weise zugegeben, und zwar in Gehalten zwischen 0,01 und 0,14 %. Konkret können Gehalte wie folgt in der Legierung eingestellt werden:
- 0,04-0,14%
- 0,04-0,10%.
- 0.04 to 0.14%
- 0.04-0.10%.
Auch Magnesium zählt zu den Zugabeelementen in Gehalten 0,0005 bis 0,05 %. Konkret besteht die Möglichkeit, dieses Element wie folgt in der Legierung einzustellen:
- 0,001-0,05%
- 0,008-0,05%.
- 0.001-0.05%
- From 0.008 to 0.05%.
Die Elemente Schwefel und Bor können in der Legierung wie folgt gegeben sein:
Die Legierung kann des Weiteren Kalzium in Gehalten zwischen 0,0005 und 0,07 %, insbesondere 0,001 bis 0,05 % oder 0,01 bis 0,05 %, beinhalten.The alloy may further include calcium at levels between 0.0005 and 0.07%, especially 0.001 to 0.05% or 0.01 to 0.05%.
Sofern die Wirksamkeit des reaktiven Elementes Lanthan allein nicht ausreichen sollte, um die in der Aufgabenstellung dargelegten Werkstoffeigenschaften zu erzeugen, kann die Legierung des Weiteren mindestens eines der Elemente Ce, Y, Zr, Hf, Ti mit einem Gehalt von 0,01 bis 0,3 % enthalten, die bedarfsweise auch definierte Zugaben sein können.If the effectiveness of the reactive element lanthanum alone should not be sufficient to produce the material properties set out in the problem, the alloy may further comprise at least one of the elements Ce, Y, Zr, Hf, Ti with a content of 0.01 to 0, 3%, which can also be defined supplements as needed.
Zusätze von Sauerstoff affinen Elementen wie La, Ce, Y, Zr, Hf, Ti verbessern die Lebensdauer. Sie tun dies, indem sie in die Oxidschicht mit eingebaut werden und dort auf den Korngrenzen die Diffusionswege des Sauerstoffs blockieren. Die Menge der für diesen Mechanismus zur Verfügung stehenden Elemente muss deshalb auf das Atomgewicht normiert werden, um die Mengen unterschiedlicher Elemente untereinander vergleichen zu können.Additions of oxygen-affinity elements such as La, Ce, Y, Zr, Hf, Ti improve the lifetime. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries. The amount of elements available for this mechanism must therefore be normalized to the atomic weight in order to be able to compare the amounts of different elements among each other.
Das Potential der wirksamen Elemente (PwE) wird deshalb zu
definiert, wobei E das betreffende Element und XE der Gehalt des betreffenden Elementes in Prozent ist.The potential of the active elements (PwE) therefore becomes too high
where E is the relevant element and X E is the content of that element in percent.
Wie bereits angesprochen, kann die Legierung 0,01 bis 0,3 % jeweils eines oder mehrerer der Elemente La, Ce, Y, Zr, Hf, Ti beinhalten, wobei die
insbesondere ≤ 0,36 (bei 0,01 bis 0,2 % des gesamten Elements) ist, worin PwE dem Potential der wirksamen Elemente entspricht.As already mentioned, the alloy may contain 0.01 to 0.3% of one or more of the elements La, Ce, Y, Zr, Hf, Ti, respectively
in particular ≤ 0.36 (at 0.01 to 0.2% of the total element), where PwE corresponds to the potential of the active elements.
Alternativ besteht bei Vorhandensein mindestens eines der Elemente La, Ce, Y, Zr, Hf, Ti in Gehalten von 0,02 bis 0,10 % die Möglichkeit, dass die Summe PwE =
1,43 Xce + 1,49 · XLa + 2,25 XY +2,19 · Xzr +1,12 XHf + 4,18 · XTi kleiner gleich 0,36 ist, worin PwE dem Potential der wirksamen Elemente entspricht.Alternatively, in the presence of at least one of the elements La, Ce, Y, Zr, Hf, Ti in contents of 0.02 to 0.10%, there is the possibility that the sum PwE =
1.43 X ce + 1.49 × X La + 2.25 X Y + 2.19 × X zr + 1.12 X Hf + 4.18 × X Ti is less than or equal to 0.36 where PwE is the potential of corresponds to effective elements.
Die Legierung kann darüber hinaus einen Phosphorgehalt zwischen 0,001 bis 0,020%, insbesondere von 0,005 bis 0,020 % aufweisen.In addition, the alloy can have a phosphorus content between 0.001 to 0.020%, in particular from 0.005 to 0.020%.
Des Weiteren kann die Legierung zwischen 0,01 bis 1,0 % jeweils eines oder mehrerer der Elemente Mo, W, V, Nb, Ta, Co enthalten, die darüber hinaus noch wie folgt eingeschränkt werden können:
- 0,01
0,2 %bis - 0,01
bis 0,06 %.
- 0.01 to 0.2%
- 0.01 to 0.06%.
Schließlich können an Verunreinigungen noch die Elemente Kupfer, Blei, Zink und Zinn in Gehalten wie folgt gegeben sein:
Die erfindungsgemäße Legierung soll für den Einsatz in elektrischen Heizelementen verwendet werden, insbesondere in elektrischen Heizelementen, die eine hohe Formstabilität und ein geringes Sagging erfordern.The alloy according to the invention is to be used for use in electric heating elements, in particular in electrical heating elements which require high dimensional stability and low sagging.
Ein konkreter Anwendungsfall für die erfindungsgemäße Legierung ist der Einsatz im Ofenbau.A concrete application for the alloy according to the invention is the use in furnace construction.
Anhand der nachfolgenden Beispiele wird der Erfindungsgegenstand näher erläutert.Based on the following examples, the subject invention will be explained in more detail.
Die Tabellen 1 bis 3 spiegeln - wie bereits eingangs angeführt - den Stand der Technik wider.Tables 1 to 3 reflect - as already mentioned at the beginning - the state of the art.
In den Tabellen 4a und 4b sind großtechnisch erschmolzene Eisen-Nickel-Chrom-Silizium-Legierungen nach dem Stand der Technik T1 bis T7, eine im Labormaßstab erschmolzene Legierung nach dem Stand der Technik T8 und mehrere im Labormaßstab erschmolzene erfindungsgemäße Versuchslegierungen V771 bis V777, V1070 bis V1076, V1090 bis V1093 zur Optimierung der Legierungszusammensetzung dargestellt.In Tables 4a and 4b are industrially molten iron-nickel-chromium-silicon alloys according to the prior art T1 to T7, one on a laboratory scale Prior art molten alloy T8 and a plurality of bench scale inventive experimental alloys V771 to V777, V1070 to V1076, V1090 to V1093 melted to optimize the alloy composition.
Bei den im Labormaßstab erschmolzenen Legierungen T8, V771-V777, V1070-V1076, V1090 - V1093 wurde aus dem in Blöcken abgegossenen Material mittels Warmwalzen, Kaltziehen und passenden Zwischen- bzw. Endglühungen ein weich geglühter Draht mit dem Durchmesser 1,29 mm hergestellt.For the T8, V771-V777, V1070-V1076, V1090-V1093 alloys melted on a laboratory scale, a soft annealed wire of diameter 1.29 mm was produced from the material cast in blocks by hot rolling, cold drawing and appropriate intermediate or final annealing.
Bei den großtechnisch erschmolzenen Legierungen T1-T7 wurde aus der großtechnischen Fertigung ein betrieblich gefertigtes und weich geglühtes Muster mit dem Durchmesser 1,29 mm entnommen. Für den Lebensdauertest wurde eine kleinere Teilmenge des Drahtes jeweils im Labormaßstab bis an 0,4 mm gezogen.For the large-scale molten alloys T1-T7, a factory-made and soft-annealed pattern with a diameter of 1.29 mm was taken from large-scale production. For the life test, a smaller subset of the wire was drawn on a laboratory scale up to 0.4 mm.
Für Heizleiter in Form von Draht sind beschleunigte Lebensdauertests zum Vergleich von Werkstoffen untereinander zum Beispiel mit den folgenden Bedingungen möglich und üblich:For heating conductors in the form of wire accelerated life tests for comparing materials with each other, for example, with the following conditions are possible and common:
Der Heizleiter-Lebensdauertest wird an Drähten mit dem Durchmesser 0,40 mm durchgeführt. Der Draht wird zwischen 2 Stromzuführungen im Abstand von 150 mm eingespannt und durch Anlegen einer Spannung bis auf 1150°C erhitzt. Die Erhitzung auf 1150°C erfolgt jeweils für 2 Minuten, dann wird die Stromzufuhr für 15 Sekunden unterbrochen. Am Ende der Lebensdauer versagt der Draht dadurch, dass der restliche Querschnitt durchschmilzt. Die Brenndauer ist die Addition der "an"-Zeiten während der Lebensdauer des Drahtes. Die relative Brenndauer tb ist die Angabe in % bezogen auf die Brenndauer einer Referenzcharge.The heat conductor life test is carried out on wires with a diameter of 0.40 mm. The wire is clamped between 2 power supply lines at a distance of 150 mm and heated by applying a voltage up to 1150 ° C. The heating at 1150 ° C takes place for 2 minutes, then the power supply is interrupted for 15 seconds. At the end of the life of the wire fails by the fact that the remaining cross-section melts through. The burning time is the addition of the "on" times during the life of the wire. The relative burning time tb is the indication in% related to the burning time of a reference batch.
Für die Untersuchung der Formstabilität wird in einem Saggingtest das Absenkungsverhalten (Sagging) von Heizwendeln bei der Anwendungstemperatur untersucht. Hierbei wird an Heizwendeln das Absacken der Wendeln von der Waagerechten nach einer bestimmten Zeit erfasst. Je geringer die Absackung, desto größer ist die Formstabilität bzw. Kriechbeständigkeit des Materials.For the investigation of dimensional stability, the sagging behavior of heating coils at the application temperature is investigated in a sagging test. This is on heating coils, the sagging of the helices of the Horizontal captured after a certain time. The lower the sag, the greater the dimensional stability or creep resistance of the material.
Für diesen Versuch wird weich geglühter Draht mit dem Durchmesser 1,29 mm zu Spiralen mit dem Innendurchmesser 14 mm gewickelt Insgesamt werden für jede Charge 6 Heizwendeln mit jeweils 31 Windungen hergestellt. Alle Heizwendeln werden zu Versuchsbeginn auf eine einheitliche Ausgangstemperatur von 1000°C geregelt. Die Temperatur wird mit einem Pyrometer bestimmt. Der Versuch wird mit einem Schaltzyklus von 30 s "an" / 30 s "aus" bei konstanter Spannung durchgeführt. Nach 4 Stunden wird der Versuch beendet. Nach Abkühlung der Heizwendeln wird die Absackung der einzelnen Windungen aus der Waagerechten gemessen und der Mittelwert der 6 Werte gebildet. Diese Werte (mm) sind in Tabelle 4b eingetragen.For this test, soft annealed wire with a diameter of 1.29 mm is wound into spirals with an internal diameter of 14 mm. In total, 6 heating coils each with 31 turns are produced for each batch. All heating coils are controlled at the start of the experiment to a uniform outlet temperature of 1000 ° C. The temperature is determined with a pyrometer. The test is carried out with a switching cycle of 30 s "on" / 30 s "off" at constant voltage. After 4 hours, the experiment is terminated. After the heating coils have cooled, the sagging of the individual turns from the horizontal is measured and the mean value of the 6 values is formed. These values (mm) are listed in Table 4b.
In Tabelle 4a und 4b sind Beispiele für die Legierungen gemäß Stand der Technik T1 bis T7 aufgelistet. T1 und T2 sind Legierungen mit ca. 30 % Nickel, ca. 20 % Cr und ca. 2 % Si. Sie enthalten Zugaben von seltenen Erden (SE) in diesem Fall Cer-Mischmetall, was bedeutet, dass SE aus ca. 60 % Ce, ca. 35 % La und der Rest Pr und Nd besteht. Die relative Brenndauer beträgt 24 % bzw. 35 %.Examples of the alloys according to the prior art T1 to T7 are listed in Tables 4a and 4b. T1 and T2 are alloys with about 30% nickel, about 20% Cr and about 2% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE consists of about 60% Ce, about 35% La and the rest Pr and Nd. The relative burning time is 24% or 35%.
Das Beispiel T3 ist eine Legierung mit ca. 40 % Nickel, ca. 20 % Cr und ca. 1,3 % Si. Sie enthält Zugaben von seltenen Erden (SE) in diesem Fall Cer-Mischmetall, was bedeutet, dass SE ca. 60 % Ce, ca. 35 % La und der Rest Pr und Nd ist. Die relative Brenndauer liegt bei 72 %.The example T3 is an alloy with about 40% nickel, about 20% Cr and about 1.3% Si. It contains rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is 72%.
Die Beispiele T4 bis T7 sind Legierungen mit ca. 60 % Nickel, ca. 16 % Cr und ca. 1,2 - 1,5 % Si. Sie enthalten Zugaben von seltenen Erden (SE) in diesem Fall Cer-Mischmetall, was bedeutet, dass SE ca. 60 % Ce, ca. 35 % La und der Rest Pr und Nd ist. Die relative Brenndauer liegt im Bereich von etwa 100 bis 130 %.Examples T4 to T7 are alloys with about 60% nickel, about 16% Cr and about 1.2-1.5% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is in the range of about 100 to 130%.
Des Weiteren enthalten die Tabellen 4a und 4b eine Reihe von im Labormaßstab erschmolzene Legierungen. Die im Labormaßstab erschmolzene Legierung nach dem Stand der Technik T8 ist eine Legierung mit 36,2 % Nickel, 20,8 % Cr und 1,87 % Si.Furthermore, Tables 4a and 4b contain a number of alloys melted on a laboratory scale. The laboratory-scale melted prior art alloy T8 is an alloy of 36.2% nickel, 20.8% Cr, and 1.87% Si.
Sie enthält wie die großtechnisch hergestellten Legierungen T1-T7 Zugaben von seltenen Erden (SE) in Form von Cer-Mischmetall, was bedeutet, dass SE ca. 60 % Ce, ca. 35 % La und der Rest Pr und Nd ist und wurde, abgesehen vom Ni-, Cr-, und Si-Gehalt, nach den gleichen Vorgaben wie die großtechnischen Chargen erschmolzen. Die Chargen nach dem Stand der Technik T1 bis T8 sind damit unmittelbar vergleichbar. Die relative Brenndauer von T8 beträgt 53 %.Like the industrially produced alloys T1-T7, it contains rare earth (SE) additions in the form of cerium misch metal, which means that SE is and was about 60% Ce, about 35% La and the rest Pr and Nd, apart from the Ni, Cr, and Si contents, melted to the same specifications as the large-scale batches. The batches according to the prior art T1 to T8 are thus directly comparable. The relative burning time of T8 is 53%.
Bei den im Labormaßstab erschmolzenen erfindungsgemäßen Versuchslegierungen V771 bis V777, V1070 bis V1076, V1090 bis V1093 beträgt der Ni-Gehalt ca. 36 %, der Cr-Gehalt ca. 20 % und der Si-Gehalt ca. 1,8 %. Variiert wurden die Zugaben an Ce, La, Y, Zr, Hf, Ti, Al, Ca, Mg C, N. Diese Chargen lassen sich deshalb unmittelbar mit den Legierungen nach dem Stand der Technik T8 vergleichen, die damit als Referenzlegierung für die Optimierung dient.In the case of the trial alloys V771 to V777, V1070 to V1076, V1090 to V1093 melted on a laboratory scale according to the invention, the Ni content is about 36%, the Cr content about 20% and the Si content about 1.8%. The additions to Ce, La, Y, Zr, Hf, Ti, Al, Ca, Mg C, N were varied. These batches can therefore be compared directly with the prior art alloys T8, thus serving as a reference alloy for optimization serves.
Die Zugabe von Ce und La in V771 bis V777, V1070, V1071 und V1076 erfolgt durch eine Zugabe von Cer-Mischmetall. Diese Chargen enthalten deshalb neben Ce und La noch geringfügige Mengen an Pr und Nd, die aber wegen Ihrer geringfügigen Mengenanteile nicht explizit in Tabelle 4a aufgeführt worden sind.The addition of Ce and La in V771 to V777, V1070, V1071 and V1076 is carried out by adding cerium mischmetal. Therefore, these batches contain not only Ce and La but also minor amounts of Pr and Nd, but because of their minor proportions have not been explicitly listed in Table 4a.
Wie schon erwähnt verbessern Zusätze von Sauerstoff affinen Elementen die Lebensdauer. Sie tun dies, indem sie in die Oxidschicht mit eingebaut werden und dort auf den Korngrenzen die Diffusionswege des Sauerstoffs blockieren. Die Menge der für diesen Mechanismus zur Verfügung stehenden Elemente muss deshalb auf das Atomgewicht normiert werden, um die Mengen unterschiedlicher Elemente untereinander vergleichen zu können.As already mentioned, additions of oxygen-affine elements improve the lifetime. They do this by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries. The amount of elements available for this mechanism must therefore be normalized to the atomic weight in order to be able to compare the amounts of different elements among each other.
Das Potential der wirksamen Elemente PwE wird deshalb zu
Beim Vergleich von T6 mit T7 fällt auf, dass der Gehalt an SE gleich ist, T7 allerdings trotz einer leicht größeren Lebensdauer einen kleineren Gehalt an Ca und Mg hat. Bei Anwesenheit von SE bzw. Ce oder La scheinen Ca und Mg nicht mehr zu den wirksamen Elementen zu gehören. Da in den Laborschmelzen ohne SE bzw. Ce oder La Ca bzw. Mg immer kleiner gleich 0,001 % ist, werden diese beiden Elemente nicht in das Potential der wirksamen Elemente einbezogen.When comparing T6 with T7, it is noticeable that the content of SE is the same, but T7 has a smaller content of Ca and Mg despite a slightly longer service life. In the presence of SE, Ce or La, Ca and Mg no longer appear to belong to the active elements. Since in laboratory melts without SE or Ce or La Ca or Mg is always less than or equal to 0.001%, these two elements are not included in the potential of the active elements.
Die Addition für das Potential der wirksamen Elemente PwE ist deshalb über Ce, La, Y, Zr, Hf und Ti ausgeführt worden. Ist keine Angabe für Ce und La vorhanden, sondern auf Grund der Zugabe von Cer-Mischmetall nur die pauschale Angabe SE gegeben, so wird für die Berechnung von PwE Ce = 0,6 SE und La = 0,35 SE angenommen.
Bei den Legierungen nach dem Stand der Technik T1 bis T8 liegt PwE zwischen 0,11 (T2 und T4) und 0,15 (T6 und T7). Die Legierung nach dem Stand der Technik T8, die zugleich die Referenzlegierung für die Versuchsschmelzen ist, hat einen PwE von 0,12.In the prior art alloys T1 to T8, PwE is between 0.11 (T2 and T4) and 0.15 (T6 and T7). The prior art alloy T8, which is also the reference alloy for the trial melts, has a PwE of 0.12.
Die Versuchsschmelzen V1090 und V1072, bei denen kein Cer-Mischmetall, d. h. kein Ce und La zugegeben wurde, sondern stattdessen Y, zeigen eine geringere relative Brenndauer als T8, obwohl V1090 mit 0,10 ein leicht geringeres PwE, dafür aber V1072 mit 0,18 ein höheres PwE hat. Y scheint nicht so gut zu wirken wie Ce und/oder La, so dass ein Ersatz von SE durch Y zu einer Verschlechterung gegenüber dem Stand der Technik führt. Durch weitere Zugaben von Zr und Ti (V1074) bzw Zr und Hf (V1092, V1073, V1091, V1093) in unterschiedlichen Mengenanteilen ist es gelungen, die Lebensdauer von T8 wieder zu erreichen. Dafür war aber in allen Fällen ein PwE von größer 0,28 erforderlich (0,28 für V1092 und V1073; 0,50 für V1074; 0,33 für V1091 und 0,42 für V1093). Dies erhöht die Kosten durch einen höheren Bedarf an teuren Sauerstoff affinen Elementen und ist deshalb kein vorteilhafter Weg.Trials V1090 and V1072, which did not add cerium mischmetal, ie Ce and La, but Y instead, show a lower relative burn time than T8, although V1090 at 0.10 has a slightly lower PwE but V1072 at 0, 18 has a higher PwE. Y does not appear to work as well as Ce and / or La, so replacement of SE by Y leads to a deterioration over the prior art. Further additions of Zr and Ti (V1074) or Zr and Hf (V1092, V1073, V1091, V1093) in different proportions have succeeded in achieving the service life of T8 again. However, in all cases a PwE of greater than 0.28 was required (0.28 for V1092 and V1073, 0.50 for V1074, 0.33 for V1091 and 0.42 for V1093). This increases the cost by increasing the demand for expensive oxygen affinity elements and is therefore not an advantageous route.
Die Versuchsschmelzen V771 bis V777, V1070, V1071 sind alle mit Cer-Mischmetall erschmolzen worden, V1075 enthält nur La. Die Versuchsschmelzen V1075 und V777 erreichten von diesen Versuchsschmelzen die höchste relative Brenndauer von ca. 70 %. Das PwE von V777 ist mit 0,36 deutlich größer als in V1075 mit 0,20, das an der Grenze des PwE der Legierungen nach dem Stand der Technik liegt. Hierdurch wird ersichtlich, dass eine hohe Menge an Sauerstoff affinen Elementen nicht ausschlaggebend ist, um eine hohe relative Brenndauer zu erreichen, sondern es viel wichtiger ist, definierte Sauerstoff affine Elemente zuzufügen. Eine ähnlich gute relative Brenndauer ist mit V777 mit einer Kombination von 0,06% Ce, 0,02 % La, 0,03 % Zr und 0,04 % Ti erreicht worden. Allerdings wird dafür ein weitaus größeres PwE von 0,36 benötigt als bei V1075. Für V772 ist die relative Brenndauer leicht niedriger als bei V1075 und V777, obwohl die gleiche Menge La wie in V1075 enthalten ist. PwE ist mit 0,53 sehr hoch. Ein zu hoher Gehalt an Sauerstoff affinen Elementen führt zu verstärkter innerer Oxidation und damit im Endeffekt zu einer Verkürzung der relativen Brenndauer. Eine deutliche Überschreitung eines PwE von 0,36 erscheint damit nicht sinnvoll zu sein. V771 hat mit 0,23 einen nur wenig größeren PwE wie V1075, allerdings eine deutlich geringere relative Brenndauer. In V771 besteht ein Großteil der Sauerstoff affinen Elemente aus Ce und nur der kleinere Teil aus La. Demnach scheint es so, dass La als Brenndauer verbessernder Zusatz sehr viel wirksamer ist als Ce. Dies kann anscheinend auch nicht durch eine starke Erhöhung sowohl von Ce auf 0,17 % als auch von La auf 0,08 % ausgeglichen werden, wie V773 mit einer fast gleichen relativen Brenndauer von 58 % zeigt bei einem erhöhtem PwE von 0,36. Dies bestätigt die schon vorher getroffene Aussage dass ein PwE von deutlich größer als 0,36 nicht sinnvoll ist. Aber auch bei einem PwE von 0,22 wie bei V776 mit einer relativen Brenndauer von 59 % scheint eine Kombination von Ce = 0,06 % und La = 0,02 % und Zr = 0,05 % nicht so wirksam, wie die Zugabe von nur La bei V1075, was bedeutet, dass auch Zr nicht so wirksam ist wie La. Das Gleiche gilt für eine zusätzlich Zugabe von Y zu Ce und La, wie V774 (PwE = 0,28) zeigt und eine Kombination von Ce, La, Zr und Hf, wie V1070 (PwE = 0,19) zeigt. Eine Erhöhung von PwE um das 1,7-fache auf 0,32 für die Kombination Ce, La, Zr und Hf bringt nur eine Verlängerung der relativen Brenndauer um das 1,15-fache bei V1076, was wiederum zeigt, das zu hohe PwEs nicht mehr so wirksam sind. Dies wird noch einmal deutlich bei dem Vergleich von V1071 mit V777. V1071 hat den gleichen Gehalt an Ce, La, Zr, wie V777, nur einen deutlich höheren Ti-Gehalt, was ein PwE von 0,44 bedeutet und eine im Vergleich zu V777 deutlich herabgesetzte Brenndauer von nur 49 %. V775 mit 0,07 % Ce und 0,03 % La, 0,05 % Y und 0,03 % Hf mit einer PwE von 0,30 hat nur eine relative Brenndauer von 46 %, was zeigt, dass zusätzliche Gaben von Y und Zr zu Ce und La nicht so wirksam sind.The test melts V771 to V777, V1070, V1071 have all been melted with cerium mischmetal, V1075 contains only La. The experimental melts V1075 and V777 achieved the highest relative burning time of about 70% of these experimental melts. The PwE of V777 is significantly larger at 0.36 than in V1075 at 0.20, which is at the limit of the PwE of the prior art alloys. As a result, it can be seen that a high amount of oxygen affinity elements is not essential to achieve a high relative burning time, but it is much more important to add defined oxygen affine elements. A similar good burning time was achieved with V777 with a combination of 0.06% Ce, 0.02% La, 0.03% Zr and 0.04% Ti. However, this requires a much larger PwE of 0.36 than V1075. For V772, the relative burn time is slightly lower than for V1075 and V777, although the same amount of La as in V1075 is included. PwE is very high at 0.53. Too high a content of oxygen affine elements leads to increased internal oxidation and thus in the end to a shortening of the relative burning time. A clear overshoot of a PwE of 0.36 does not seem to make sense. At 0.23 V771 has only a slightly larger PwE like V1075, but a much lower relative burning time. In V771, most of the oxygen affinity elements are Ce and only the smaller part is La. Thus, it appears that La as a burn-time improving additive is much more effective than Ce. It also appears that this can not be compensated for by a sharp increase of both Ce to 0.17% and La to 0.08%, as shown by V773 with an almost equal relative burn time of 58% and an increased PwE of 0.36. This confirms the previously made statement that a PwE of significantly greater than 0.36 does not make sense. However, even at a PwE of 0.22 as in V776 with a relative burning time of 59%, a combination of Ce = 0.06% and La = 0.02% and Zr = 0.05% does not seem as effective as the addition from just La at V1075, which means that Zr is not as effective as La. The same applies to an additional addition of Y to Ce and La, as shown by V774 (PwE = 0.28) and a combination of Ce, La, Zr and Hf, such as V1070 (PwE = 0.19). A 1.7 fold increase in PwE to 0.32 for the Ce, La, Zr, and Hf combination only adds 1.15 times the relative burn time to V1076, again indicating that the PwEs are too high not so effective anymore. This becomes clear once again when comparing V1071 with V777. V1071 has the same content of Ce, La, Zr, as V777, only a much higher Ti content, which means a PwE of 0.44 and compared to V777 significantly reduced burning time of only 49%. V775 with 0.07% Ce and 0.03% La, 0.05% Y and 0.03% Hf with a PwE of 0.30 only has a relative burning time of 46%, indicating that additional doses of Y and Zr to Ce and La are not as effective.
In Tabelle 4b ist das Sagging zusammen mit der Korngröße der Drähte zusammengefasst. Die Legierungen nach dem Stand der Technik T1 bis T8 zeigen ein Sagging zwischen 4,5 und 6,2 mm bei vergleichbaren Korngrößen zwischen 20 und 25 µm.Table 4b summarizes sagging along with the grain size of the wires. The alloys of the prior art T1 to T8 show sagging between 4.5 and 6.2 mm at comparable grain sizes between 20 and 25 microns.
Ein höherer C- bzw. N-Gehalt verringert also das Sagging so stark, dass der das Sagging erhöhende Effekt einer kleineren Korngröße nicht vollständig kompensiert wird. Die Versuchslegierungen sind alle einer Standardwärmebehandlung unterzogen worden.A higher C- or N-content thus reduces sagging so much that the sagging-enhancing effect of a smaller grain size is not fully compensated. The trial alloys have all been subjected to a standard heat treatment.
Wie Tabelle 4b zeigt, entstehen insbesondere bei einem C-Gehalt größer 0,04 % kleinere Korngrößen. Bei Veränderung der Standardwärmebehandlung zu leicht höheren Temperaturen, bei der dann größere Korngrößen entstehen, kann bei diesen Legierungen mit einem C-Gehalt größer als 0,04% eine weitere Verminderung des Saggings erreichen werden.As Table 4b shows, especially at a C content greater than 0.04% smaller particle sizes. By changing the standard heat treatment to slightly higher temperatures, which then results in larger grain sizes, a further reduction of the sagging can be achieved in these alloys with a C content greater than 0.04%.
Die Legierung V777 zeigt das geringste Sagging von allen Legierungen. Sie hat den höchsten C-Gehalt und einen N-Gehalt im oberen Drittel. Ein hoher C-Gehalt scheint demnach besonders wirksam bei der Verringerung des Saggings zu sein.The alloy V777 shows the lowest sagging of all alloys. It has the highest C content and an N content in the upper third. A high C content therefore seems to be particularly effective in reducing sagging.
Nickelgehalte unterhalb von 34 % verschlechtern die Lebensdauer (relative Brenndauer), den spezifischen elektrischen Widerstand und den ct-Wert zu sehr. Deshalb ist 34 % die untere Grenze für den Nickelgehalt. Zu hohe Nickelgehalte verursachen auf Grund des hohen Nickelpreises höhere Kosten. Deshalb soll 42 % die obere Grenze für den Nickel-Gehalt sein.Nickel contents below 34% degrade the lifetime (relative burning time), the electrical resistivity and the ct value too much. Therefore, 34% is the lower limit for the nickel content. Too high nickel contents cause higher costs due to the high nickel price. Therefore, 42% should be the upper limit for the nickel content.
Zu niedrige Cr-Gehalte bedeuten, dass die Cr-Konzentration zu schnell unter die kritische Grenze sinkt. Deshalb ist 18 % Cr die untere Grenze für Chrom. Zu hohe Cr-Gehalte verschlechtern die Verarbeitbarkeit der Legierung. Deshalb ist 26 % Cr die obere Grenze.Too low Cr contents mean that the Cr concentration falls too fast below the critical limit. That is why 18% Cr is the lower limit for chromium. Too high Cr contents deteriorate the workability of the alloy. Therefore, 26% Cr is the upper limit.
Die Bildung einer Siliziumoxidschicht unterhalb der Chromoxidschicht verringert die Oxidationsrate. Unterhalb von 1 % ist die Siliziumoxidschicht zu lückenhaft, um Ihre Wirkung voll zu entfalten. Zu hohe Si-Gehalte beeinträchtigen die Verarbeitbarkeit der Legierung. Deshalb ist ein Si-Gehalt von 2,5 % die obere Grenze.The formation of a silicon oxide layer below the chromium oxide layer reduces the oxidation rate. Below 1%, the silicon oxide layer is too patchy to your To be fully effective. Too high Si contents impair the processability of the alloy. Therefore, an Si content of 2.5% is the upper limit.
Es ist ein Mindestgehalt von 0,01 % La notwendig, um die die Oxidationsbeständigkeit steigernde Wirkung des La zu erhalten. Die Obergrenze wird bei 0,26 % gelegt, was einem PwE von 0,38 entspricht. Größere Werte von PwE sind, wie in den Beispielen erläutert, nicht sinnvoll.A minimum content of 0.01% La is necessary to obtain the oxidation resistance-enhancing effect of La. The upper limit is set at 0.26%, which corresponds to a PwE of 0.38. Larger values of PwE are not meaningful as explained in the examples.
Al wird zur Verbesserung der Verarbeitbarkeit der Legierung benötigt. Es ist deshalb ein Mindestgehalt von 0,05 % notwendig. Zu hohe Gehalte wiederum beeinträchtigen die Verarbeitbarkeit. Der Al-Gehalt ist deshalb auf 1 % beschränkt.Al is needed to improve the processability of the alloy. It is therefore necessary a minimum content of 0.05%. Too high contents in turn affect the processability. The Al content is therefore limited to 1%.
Es ist ein Mindestgehalt von 0,01 % C für eine gute Formstabilität bzw. ein geringes Sagging notwendig. C wird auf 0,14 % begrenzt, da dieses Element die Oxidationsbeständigkeit und die Verarbeitbarkeit reduziert.A minimum content of 0.01% C is necessary for good dimensional stability or low sagging. C is limited to 0.14% because this element reduces oxidation resistance and processability.
Es ist ein Mindestgehalt von 0,01 % N für eine gute Formstabilität bzw. ein geringes Sagging notwendig. N wird auf 0,14 % begrenzt, da dieses Element die Oxidationsbeständigkeit und die Verarbeitbarkeit reduziert.A minimum content of 0.01% N is necessary for good dimensional stability or low sagging. N is limited to 0.14% because this element reduces oxidation resistance and processability.
Für Mg ist ein Mindestgehalt von 0,0005 % erforderlich, da hierdurch die Verarbeitbarkeit des Werkstoffs verbessert wird. Der Grenzwert wird bei 0,05 % festgelegt, um den positiven Effekt dieses Elements nicht aufzuweichen.For Mg, a minimum content of 0.0005% is required as it improves the processability of the material. The threshold is set at 0.05%, so as not to soften the positive effect of this element.
Die Gehalte Schwefel und Bor sollten so gering wie möglich gehalten werden, da diese grenzflächenaktiven Elemente die Oxidationsbeständigkeit beeinträchtigen. Es werden deshalb max. 0,01 % S und max. 0,005 % B festgelegt.The levels of sulfur and boron should be kept as low as possible, since these surface-active elements affect the oxidation resistance. It will therefore max. 0.01% S and max. 0.005% B is set.
Kupfer wird auf max. 1 % begrenzt, da dieses Element die Oxidationsbeständigkeit reduziert.Copper is heated to max. 1% limited as this element reduces the oxidation resistance.
Pb wird auf max. 0,002 % begrenzt, da dieses Element die Oxidationsbeständigkeit reduziert. Das Gleiche gilt für Sn.Pb is set to max. 0.002% limited because this element reduces the oxidation resistance. The same applies to Sn.
Es ist ein Mindestgehalt von 0,01 % Mn zur Verbesserung der Verarbeitbarkeit notwendig. Mangan wird auf 1 % begrenzt, da dieses Element die Oxidationsbeständigkeit reduziert.
20°C
900°C
20 ° C
900 ° C
Claims (38)
- An iron-nickel-chromium-silicium alloy comprising, in % by mass, 34 to 42 % nickel, 18 to 26 % chromium, 1.0 to 2.5 % silicium and additions of 0.05 to 1 % Al, 0.01 to 1 % Mn, 0.01 to 0.26 % lanthanum, 0.0005 to 0.05 % magnesium, 0.01 to 0.14 % carbon, 0.01 to 0.14 % nitrogen, max. 0.01 % sulphur, max. 0.005 % B, optionally 0.0005 to 0.07 % Ca, optionally at least one of the elements Ce, Y, Zr, Hf, Ti in a concentration of 0.01 to 0.3 %, optionally 0.001 to 0.020 % phosphorus, optionally 0.01 to 1.0 % of respectively one or more of the elements Mo, W, V, Nb, Ta, Co, the rest being iron and the usual method dependent impurities.
- An alloy according to claim 1 comprising a nickel content of 34 to 39 %.
- An alloy according to claim 1 comprising a nickel content of 34 to 38 %.
- An alloy according to claim 1 comprising a nickel content of 34 to 37 %.
- An alloy according to claim 1 comprising a nickel content of 37 to 38 %.
- An alloy according to one of the claims 1 through 5 comprising a chromium content of 20 to 24 %.
- An alloy according to one of the claims 1 through 5 comprising a chromium content of 21 to 24 %.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.5 to 2.5%.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.0 to 1.5 %.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.5 to 2.0%.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.7 to 2.5%.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.2 to 1.7%.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 1.7 to 2.2%.
- An alloy according to one of the claims 1 through 7 comprising a silicium content of 2.0 to 2.5%.
- An alloy according to one of the claims 1 through 14 comprising an aluminium content of 0.1 to 0.7 %.
- An alloy according to one of the claims 1 through 15 comprising a manganese content of 0.1 to 0.7 %.
- An alloy according to one of the claims 1 through 16 comprising a lanthanum content of 0.01 to 0.2 %.
- An alloy according to one of the claims 1 through 16 comprising a lanthanum content of 0.02 to 0.15 %.
- An alloy according to one of the claims 1 through 16 comprising a lanthanum content of 0.04 to 0.15%.
- An alloy according to one of the claims 1 through 19 comprising a nitrogen content of 0.02 to 0.10%.
- An alloy according to one of the claims 1 through 19 comprising a nitrogen content of 0.03 to 0.09 %.
- An alloy according to one of the claims 1 through 21 comprising a carbon content of 0.04 to 0.14%.
- An alloy according to one of the claims 1 through 21 comprising a carbon content of 0.04 to 0.10 %.
- An alloy according to one of the claims 1 through 23 comprising a magnesium content of 0.001 to 0.05 %.
- An alloy according to one of the claims 1 through 23 comprising a magnesium content of 0.008 to 0.05 %.
- An alloy according to one of the claims 1 through 25 comprising max. 0.005 % sulphur and max. 0.003 % B.
- An alloy according to one of the claims 1 through 26 comprising 0.001 to 0.05 % Ca.
- An alloy according to one of the claims 1 through 26 comprising 0.01 to 0.05 % Ca.
- An alloy according to one of the claims 1 through 28 comprising 0.01 to 0.3 % of respectively one or more of the elements La, Ce, Y, Zr, Hf, Ti, wherein the sum PwE = 1.43 • XCe + 1.49 • XLa + 2.25 • XY + 2.19 • XZr + 1.12 XHf + 4.18 • XTi is less than/equal to 0.38, wherein PwE corresponds to the potential of the acting elements.
- An alloy according to one of the claims 1 through 28 comprising 0.01 to 0.2 % of respectively one or more of the elements La, Ce, Y, Zr, Hf, Ti, wherein the sum PwE = 1.43 • XCe + 1.49 • XLa + 2.25 • XY + 2.19 XZr + 1.12 XHf + 4.18 • XTi is less than/equal to 0.36, wherein PwE corresponds to the potential of the acting elements.
- An alloy according to one of the claims 1 through 28 comprising 0.02 to 0.15 % of respectively one or more of the elements La, Ce, Y, Zr, Hf, Ti, wherein the sum PwE = 1.43 • XCe + 1.49 • XLa + 2.25 • XY + 2.19 • XZr + 1.12 • XHf + 4.18 • XTi is less than/equal to 0.36, wherein PwE corresponds to the potential of the acting elements.
- An alloy according to one of the claims 1 through 31 comprising a phosphorus content of 0.005 to 0.020 %.
- An alloy according to one of the claims 1 through 32 comprising 0.01 to 0.2 % of respectively one or more of the elements Mo, W, V, Nb, Ta, Co.
- An alloy according to one of the claims 1 through 32 comprising 0.01 to 0.06 % of respectively one or more of the elements Mo, W, V, Nb, Ta, Co.
- An alloy according to one of the claims 1 through 34, in which the impurities are set in concentrations of max. 1.0 % Cu, max. 0.002 % Pb, max. 0.002 % Zn, max. 0.002 % Sn.
- A use of the alloy according to one of the claims 1 through 35 for the utilization in electric heating elements.
- A use of the alloy according to one of the claims 1 through 35 for the utilization in electric heating elements which require a high dimensional stability or a low sagging.
- A use of the alloy according to one of the claims 1 through 35 for the utilization in furnace construction.
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CN104313395A (en) * | 2014-10-14 | 2015-01-28 | 杨雯雯 | Elastic alloy |
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-
2007
- 2007-01-31 DE DE102007005605A patent/DE102007005605B4/en not_active Expired - Fee Related
-
2008
- 2008-01-15 US US12/086,822 patent/US20090285717A1/en not_active Abandoned
- 2008-01-15 WO PCT/DE2008/000060 patent/WO2008092419A2/en active Application Filing
- 2008-01-15 CN CN2008800012355A patent/CN101595236B/en active Active
- 2008-01-15 PL PL08706757T patent/PL2115179T3/en unknown
- 2008-01-15 DE DE502008000536T patent/DE502008000536D1/en active Active
- 2008-01-15 MX MX2009007535A patent/MX2009007535A/en active IP Right Grant
- 2008-01-15 JP JP2009547522A patent/JP5404420B2/en active Active
- 2008-01-15 ES ES08706757T patent/ES2341151T3/en active Active
- 2008-01-15 AT AT08706757T patent/ATE463589T1/en active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012175271A2 (en) | 2011-06-21 | 2012-12-27 | Robert Bosch Gmbh | Use of a hot gas corrosion-resistant ductile alloy |
DE102011077893A1 (en) | 2011-06-21 | 2012-12-27 | Robert Bosch Gmbh | Use of a hot gas corrosion resistant ductile alloy |
WO2012175271A3 (en) * | 2011-06-21 | 2013-09-26 | Robert Bosch Gmbh | Use of a hot gas corrosion-resistant ductile alloy |
Also Published As
Publication number | Publication date |
---|---|
PL2115179T3 (en) | 2010-09-30 |
ATE463589T1 (en) | 2010-04-15 |
JP2010516902A (en) | 2010-05-20 |
CN101595236B (en) | 2011-08-31 |
CN101595236A (en) | 2009-12-02 |
WO2008092419A2 (en) | 2008-08-07 |
JP5404420B2 (en) | 2014-01-29 |
WO2008092419A3 (en) | 2008-10-16 |
EP2115179A2 (en) | 2009-11-11 |
DE102007005605B4 (en) | 2010-02-04 |
ES2341151T3 (en) | 2010-06-15 |
DE502008000536D1 (en) | 2010-05-20 |
DE102007005605A1 (en) | 2008-08-07 |
US20090285717A1 (en) | 2009-11-19 |
MX2009007535A (en) | 2009-08-20 |
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