EP2127472B1 - Utilisation d'un alliage fer-chrome-aluminium ayant une durée de vie élevée et des variations faibles de résistance à la chaleur - Google Patents
Utilisation d'un alliage fer-chrome-aluminium ayant une durée de vie élevée et des variations faibles de résistance à la chaleur Download PDFInfo
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- EP2127472B1 EP2127472B1 EP08706758A EP08706758A EP2127472B1 EP 2127472 B1 EP2127472 B1 EP 2127472B1 EP 08706758 A EP08706758 A EP 08706758A EP 08706758 A EP08706758 A EP 08706758A EP 2127472 B1 EP2127472 B1 EP 2127472B1
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- 229910000838 Al alloy Inorganic materials 0.000 title claims description 14
- -1 iron-chromium-aluminium Chemical compound 0.000 title claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 65
- 239000000956 alloy Substances 0.000 claims abstract description 64
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011888 foil Substances 0.000 claims abstract description 19
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 19
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 17
- 238000007792 addition Methods 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000001419 dependent effect Effects 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims 1
- 238000010309 melting process Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 23
- 239000010408 film Substances 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000011572 manganese Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 239000010955 niobium Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000946 Y alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- 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
- C22C38/02—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
- C22C38/04—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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
Definitions
- the invention relates to the use of an iron-chromium-aluminum alloy produced by melt metallurgy with a long service life and small changes in the heat resistance.
- Such alloys are used to make electrical heating elements and catalyst supports. These materials form a dense, adherent alumina layer that protects them from destruction at high temperatures (eg up to 1400 ° C). This protection is improved by additions of so-called reactive elements such as Ca, Ce, La, Y, Zr, Hf, Ti, Nb, V, which inter alia improve the adhesion of the oxide layer and / or reduce the layer growth, as for example in “ Ralf Bürgel, Handbuch der Hochtemperatur-Werkstofftechnik, Vieweg Verlag, Braunschweig 1998 "from page 274 is described.
- reactive elements such as Ca, Ce, La, Y, Zr, Hf, Ti, Nb, V
- the aluminum oxide layer protects the metallic material against rapid oxidation. At the same time she is growing herself, albeit very slowly. This growth takes place using consumption of the aluminum content of the material. If no aluminum is present, other oxides (chromium and iron oxides) grow, the metal content of the material is consumed very quickly and the material fails due to destructive corrosion. The time to failure is defined as the lifetime. An increase in the aluminum content prolongs the service life.
- the WO 02/20197 is a ferritic stainless steel alloy, especially for use as Bankleiterelement known.
- the alloy is formed by a powder metallurgy FeCrAl alloy comprising (in% by mass) less than 0.02% C, ⁇ 0.5% Si, ⁇ 0.2% Mn, 10.0 to 40.0% Cr, ⁇ 0.6% Ni, ⁇ 0.01% Cu, 2.0 to 10.0% Al, one or more element (s) from the group of reactive elements, such as Sc, Y, La, Ce, Ti, Zr, Hf, V, Nb, Ta, in contents between 0.1 and 1.0%, balance iron and unavoidable impurities.
- DE-A 199 28 842 is an alloy with (in wt .-%) 16 to 22% Cr, 6 to 10% Al, 0.02 to 1.0% Si, max. 0.5% Mn, 0.02 to 0.1% Hf, 0.02 to 0.1% Y, 0.001 to 0.01% Mg, max. 0.02% Ti, max. 0.03% Zr, max. 0.02% SE, max. 0.1% Sr, max. 0.1% Ca, max. 0.5% Cu, max. 0.1% V, max. 0.1% Ta, max. 0.1% Nb, max. 0.03% C, max. 0.01% N, max. 0.01% B, remainder iron and impurities due to melting for use as a carrier film for catalytic converters, as a heating conductor and as a component in industrial furnace construction and in gas burners.
- EP-B 0 387 670 becomes an alloy containing (in wt%) 20 to 25% Cr, 5 to 8% Al, 0.03 to 0.08% yttrium, 0.004 to 0.008% nitrogen, 0.020 to 0.040% carbon, and about equal parts 0.035 to 0.07% Ti and 0.035 to 0.07% zirconium, and max. 0.01% phosphorus, max. 0.01% magnesium, max. 0.5% manganese, max. 0.005% sulfur, remainder iron, wherein the sum of the contents of Ti and Zr is 1.75 to 3.5% times as large as the percentage sum of the contents of C and N as well as impurities caused by melting.
- Ti and Zr can be completely or partially replaced by hafnium and / or tantalum or vanadium.
- EP-B 0 290 719 is an alloy with (in wt .-%) 12 to 30% Cr, 3.5 to 8% Al, 0.008 to 0.10% carbon, max. 0.8% silicon, 0.10 to 0.4% manganese, max. 0.035% phosphorus, max. 0.020% sulfur, 0.1 to 1.0% molybdenum, max.
- nickel 1% nickel, and the additives 0.010 to 1.0% zirconium, 0.003 to 0.3% titanium and 0.003 to 0.3% nitrogen, calcium plus magnesium 0.005 to 0.05%, and rare earth metals from 0.003 to 0.80 %, Niobium 0.5%, remainder iron described with conventional accompanying elements, which is used for example as a wire for heating elements for electrically heated furnaces and as a construction material for thermally stressed parts and as a film for the preparation of catalyst supports.
- US-A 4,414,023 is a steel with (in wt.%) 8.0 to 25.0% Cr, 3.0 to 8.0% Al, 0.002 to 0.06% rare earth metals, max. 4.0% Si, 0.06 to 1.0% Mn, 0.035 to 0.07% Ti, 0.035 to 0.07% Zr, including unavoidable impurities.
- t B 4 . 4 ⁇ 10 - 3 ⁇ C 0 - C B ⁇ ⁇ ⁇ d ⁇ k - 1 n ⁇ ⁇ ⁇ m * 1 n - 1 where ⁇ rm * is the critical weight change at which flaking begins.
- Heating conductors which consist of thin foils (for example, approximately 20 to 300 ⁇ m thick with a width in the range of one or several millimeters), are characterized by a large surface area to volume ratio. This is advantageous if you want to achieve fast heating and cooling times, as z. B. in the heating elements used in glass ceramic panels are required to make the heating quickly visible and to achieve a rapid heating similar to a gas cooker. At the same time, however, the large surface area to volume ratio is disadvantageous for the service life of the heating conductor.
- the behavior of the hot resistor must be considered. As a rule, a constant voltage is applied to the heating conductor. If the resistance remains constant over the life of the heating element, the current and the power of this heating element will not change.
- the temperature of the heating element decreases.
- the life of the heating conductor and thus also of the heating element is extended.
- heating elements often have a lower power limit, so this effect can not be used to extend service life.
- the warm resistance R W decreases over time
- the power P increases while the voltage remains constant Heating element. As the power increases, however, the temperature also increases and thus the service life of the heating conductor or heating element is shortened. The deviations of the heat resistance as a function of time should therefore be kept within a narrow range around zero.
- the lifetime and the behavior of the heat resistance can be measured, for example, in an accelerated life test.
- Such is z. In Harald Pfeifer, Hans Thomas, Zinderfest alloys, Springer Verlag, Berlin / Göttingen / Heidelberg / 1963 on page 113 described. It is carried out with a switching cycle of 120 s, at constant temperature on helically shaped wire with a diameter of 0.4 mm. The test temperature is 1200 ° C or 1050 ° C. Since in this case the behavior of thin foils is specifically concerned, the test was modified as follows: Film strips of 50 ⁇ m thickness and 6 mm width were clamped between 2 current feedthroughs and heated to 1050 ° C. by applying a voltage.
- the heating at 1050 ° C takes place for 15 s, then the power supply is interrupted for 5 s. At the end of the life of the film fails by the fact that the remaining cross-section melts through.
- the temperature is automatically measured during the life test with a pyrometer and, if necessary, corrected by the program control to the setpoint temperature.
- the burn time is the addition of the times that the sample is heated.
- the burning time is the time to failure of the samples, the burning time the current time during an experiment.
- the burning time or burning time is given as a relative value in% relative to the burning time of a reference sample and referred to as the relative burning time or relative burning time.
- Residual iron and manufacturing impurities consists, after which a homogenization treatment is carried out at 600 to 1200 ° C and the mass of the total coating is adjusted to 0.5 to 5%.
- the film thus produced can also be used, among other things, as resistance material or heating conductor.
- the invention has for its object to provide an iron-chromium-aluminum alloy for the specific application, which has a longer life than the previously used iron-chromium-aluminum alloys, with little change in the heat resistance over time at the application temperature , in particular when used as a film in a defined dimensional range, has.
- This object is achieved by the use of an iron-chromium-aluminum alloy with a long service life and little change in the heat resistance as a foil for heating elements in the dimensional range of 0.020 to 0.300 mm thickness, with (in wt .-%) 4.5 to 6, 5% Al, 16 to 24% Cr and additions of 0.05 to 0.7% Si, 0.001 to 0.5% Mn, 0.02 to 0.1% Y, 0.02 to 0.1% Zr, 0.02 to 0.1% Hf, 0.003 to 0.020% C, max. 0.03% N, max. 0.01% S, max. 0.5% Cu, balance iron and the usual melting impurities.
- the alloy should advantageously be melted with 0.0001 to 0.05% Mg, 0.0001 to 0.03% Ca and 0.010 to 0.030% P in order to be able to set optimum material properties in the film.
- the element Y can furthermore be wholly or partially replaced by at least one of the elements Sc and / or La and / or cerium, partial ranges of 0.02 to 0.1% by weight being conceivable.
- the element Hf may be further characterized by at least one of the elements Sc and / or Ti and / or V and / or Nb and / or Ta and / or La and / or Cerium completely or partially replaced, with partial substitution ranges between 0.01 and 0.1% by mass are conceivable.
- the alloy with (in wt .-%) max. 0.02% N, and max. 0.005% S are melted.
- Preferred Fe-Cr-Al alloys for use as a heating element are characterized by the following composition (in% by weight): al 4.8 - 6.2% 5.0 - 5.8% Cr 18 - 23% 19 - 22% Si 0.05 - 0.5% 0.05 - 0.5% Mn 0.005 - 0.5% 0.005 - 0.5% Y 0.03 - 0.1% 0.03 - 0.1% Zr 0.02 - 0.08% 0.02-0.08% Hf 0.02 - 0.10% 0.02 - 0.10% C 0.003 - 0.020% 0.003 - 0.020% mg 0.0001 - 0.03% 0.0001 - 0.02% Ca 0.0001 - 0.02% 0.0001 - 0.02% P 0.010 to 0.025% 0.010 to 0.022 S Max. 0.01% Max. 0.01% N Max. 0.03% Max. 0.03% Cu Max. 0.5% Max. 0.5% Ni Max. 0.5% Max. 0.5% Not a word Max. 0.1% Max. 0.1% W Max. 0.1% Max.
- Table 1 shows industrially molten iron-chromium-aluminum alloys T1 to T3, L1 to L3 and the alloy E1 according to the invention. Films of this composition were made after melting of the alloy via block or continuous casting and hot and cold forming with required (s) intermediate annealing (s).
- Figures 1-5 each show the course of the heat resistance in the life test on films for the alloys T3, L1-L3 according to the prior art and the inventively vulnerable batch E1.
- a sample is taken with a strip thickness of 50 microns and cut to a width of about 6mm and subjected to the life test for films.
- illustration 1 shows the heat resistance curve in the above described conductor test for films on one of the iron-chromium-aluminum Aluchrom Y alloys with a composition of 20 to 22% chromium, 5 to 6% aluminum, 0.01% to 0.1% carbon, max , 0.5% Mn, max. 0.3% Si, additions of 0.01 to 0.15% Y, 0.01 to 0.1% Zr and 0.01 to 0.1% Ti, the z. B. is used as a heating element.
- the resistance is shown relative to its initial value at the beginning of the measurement. It shows a decrease in the heat resistance. Towards the end of the further course shortly before the sample burns through, the resistance to heat increases sharply (in illustration 1 from approx. 100% relative burning time).
- a W will be the maximum deviation of the heat resistance ratio from the initial value 1.0 at the beginning of Try (or shortly after the start after the formation of the contact resistance) until the beginning of the steep rise referred.
- This material typically has a relative burning time of about 100% as shown by examples T1 to T3 in Table 1.
- the results of the lifetime tests are shown in Table 1.
- the relative burning time indicated in Table 1 is formed by the mean values of at least 3 samples. Furthermore, the A W determined for each batch is entered.
- T1 to T3 are three batches of the prior art Aluchrom Y iron-chromium-aluminum alloys having a composition of about 20% chromium, about 5.2% aluminum, about 0.03% carbon, and additions of Y, Zr and Ti each about 0.05%. They achieve a relative burning time of 96% (T1) to 124% (T3) and an outstanding value for AW of -2 to -3%.
- this alloy shows an A W of -5% for L1 ( Figure 2 ) and even -8% of L2 ( Figure 3 ).
- an A W of -8% is too large and leads experience shows a significant increase in temperature of the component, which compensates for the greater life of this material, so brings no overall advantage.
- L3 is a variant of the material Aluchrom YHf according to the prior art, with an increased aluminum content of 7%.
- the relative burning time is only 153% similar to that of L2 with 5.6% Al and even smaller, than that of L1 with 5.9 % Al.
- An increase in the aluminum content to 7% does not appear to increase the life of Schuleiterfolien further.
- E1 shows an alloy, as it can be used according to the invention for films in application ranges of 0.020 to 0.300 mm thickness. It has with 189% the desired high relative burning time and with an A W of -3% at the same time a very favorable behavior of the heat resistance similar to the batches according to the prior art T1 to T3.
- E1 is an iron-chromium-aluminum alloy with 19 to 22% Cr, 5.5 to 6.5% aluminum, max. 0.5% Mn, max. 0.5% Si, max. 0.05% carbon and additions of max. 0.10% Y, max. 0.07% Zr and max. 0.1% Hf.
- it contains a very low carbon content of only 0.007%.
- L1 has an A W of -5% at a carbon content of 0.026% and an A W of -8% at a carbon content of 0.029%.
- Cu, P, Mg, Ca and V are comparable to L1 and L2 to E1.
- a minimum content of 0.02% Y is necessary to obtain the oxidation resistance-enhancing effect of Y.
- the upper limit is set at 0.1% by weight for cost reasons.
- a minimum content of 0.02% Zr is necessary to get a good life and a low A W.
- the upper limit is set for cost reasons at 0.1 1 wt .-% Zr.
- a minimum content of 0.02% Hf is necessary to obtain the oxidation resistance enhancing effect of Hf.
- the upper limit is set for cost reasons at 0.1 wt .-% Hf.
- the carbon content should be less than 0.020% to obtain a low value of A W. It should be greater than 0.003% to ensure processability.
- the nitrogen content should not exceed 0.03% in order to avoid the formation of processability deteriorating nitrides.
- the content of phosphorus should be less than 0.030% since this surfactant affects the oxidation resistance. Too low a P content increases costs. The P content is therefore greater than or equal to 0.010%.
- the levels of sulfur should be kept as low as possible because this surfactant affects the oxidation resistance. It will therefore max. 0.01% S set.
- Chromium contents between 16 and 24% by mass have no decisive influence on the service life as in J. Klöwer, Materials and Corrosion 51 (2000), pages 373-385 to read.
- a certain chromium content is necessary because chromium promotes the formation of the particularly stable and protective ⁇ - Al 2 O 3 layer. Therefore, the lower limit is 16%.
- Chromium contents> 24% complicate the processability of the alloy.
- An aluminum content of 4.5% is at least necessary to obtain an alloy with sufficient life. Al contents> 6.5% no longer increase the life span of film heating conductors.
- a minimum content of 0.001% Mn is required to improve processability.
- Manganese is limited to 0.5% because this element reduces oxidation resistance.
- Copper is heated to max. 0.5% limited as this element reduces the oxidation resistance. The same goes for nickel.
- Molybdenum is reduced to max. 0.1% limited because this element reduces the oxidation resistance. The same goes for tungsten.
- the contents of magnesium and calcium are set in the spread range of 0.0001 to 0.05 wt .-%, respectively 0.0001 to 0.03 wt .-%.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Resistance Heating (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
Claims (34)
- Utilisation d'un alliage fer-chrome-aluminium ayant une durée de vie élevée et des variations faibles de résistance à la chaleur en tant que feuille pour des éléments de chauffage dans une gamme de dimensions comprise entre 0,020 et 0,300 mm d'épaisseur comprenant (en % en poids) 4,5 à 6,5 % d'Al, 16 à 24 % de Cr et des additions de 0,05 à 0,7 % de Si, 0,001 à 0,5 % de Mn, 0,02 à 0,1 % de Y, 0,02 à 0,1 % de Zr, 0,02 à 0,1 % de Hf, 0,003 à 0,020 % de C, max. 0,03 % de N, max. 0,01 % de S, max. 0,5 % de Cu, le reste étant du fer et des impuretés usuelles résultant de l'élaboration.
- Utilisation de l'alliage selon la revendication 1, comprenant (en % en poids) 4,8 à 6,2 % d'Al.
- Utilisation de l'alliage selon la revendication 1 ou la revendication 2, comprenant (en % en poids) 5,0 à 5,8 % d'Al.
- Utilisation de l'alliage selon la revendication 1 ou la revendication 2, comprenant (en % en poids) 4,8 à 5,5 % d'Al.
- Utilisation de l'alliage selon la revendication 1, comprenant (en % en poids) 5,5 à. 6,3 % d'Al.
- Utilisation de l'alliage selon l'une des revendications 1 à 5, comprenant (en % en poids) 18 à 23 % de Cr.
- Utilisation de l'alliage selon l'une des revendications 1 à 6, comprenant (en % en poids) 19 à 22 % de Cr.
- Utilisation de l'alliage selon l'une des revendications 1 à 7, comprenant (en % en poids) des additions de 0,05 à 0,5 % de Si.
- Utilisation de l'alliage selon l'une des revendications 1 à 8, comprenant (en % en poids) des additions de 0,005 à 0,5 % de Mn.
- Utilisation de l'alliage selon l'une des revendications 1 à 9, comprenant (en % en poids) des additions de 0,03 à 0,1 % de Y.
- Utilisation de l'alliage selon l'une des revendications 1 à 10, comprenant (en % en poids) des additions de 0,02 à 0,08 % de Zr.
- Utilisation de l'alliage selon l'une des revendications 1 à 11, comprenant (en % en poids) des additions de 0,02 à 0,1 % de Hf.
- Utilisation de l'alliage selon l'une des revendications 1 à 12, comprenant (en % en poids) des additions de 0,003 à 0,020 % de C.
- Utilisation de l'alliage selon l'une des revendications 1 à 13, comprenant 0,0001 à 0,05 % de Mg, 0,0001 à 0,03 % de Ca, 0,010 à 0,030 % de P.
- Utilisation de l'alliage selon l'une des revendications 1 à 14, comprenant (en % en poids) 0,0001 à 0,03 % de Mg.
- Utilisation de l'alliage selon l'une des revendications 1 à 15, comprenant (en % en poids) 0,0001 à 0,02 % de Mg.
- Utilisation de l'alliage selon l'une des revendications 1 à 16, comprenant (en % en poids) 0,0002 à 0,01 % de Mg.
- Utilisation de l'alliage selon l'une des revendications 1 à 17, comprenant (en % en poids) 0,0001 à 0,02 % de Ca.
- Utilisation de l'alliage selon l'une des revendications 1 à 18, comprenant (en % en poids) 0,0002 à 0,01 % de Ca.
- Utilisation de l'alliage selon l'une des revendications 1 à 19, comprenant (en % en poids) 0,010 à 0,025 % de P.
- Utilisation de l'alliage selon l'une des revendications 1 à 20, comprenant (en % en poids) 0,010 à 0,022 % de P.
- Utilisation de l'alliage selon l'une des revendications 1 à 21, dans lequel Y est complètement remplacé par au moins un des éléments Sc et/ou La et/ou cérium.
- Utilisation de l'alliage selon l'une des revendications 1 à 21, dans lequel Y est partiellement remplacé par (en % en poids) 0,02 à 0,10 % d'au moins un des éléments Sc et/ou La et/ou cérium.
- Utilisation de l'alliage selon l'une des revendications 1 à 23, dans lequel Hf est complètement remplacé par au moins un des éléments Sc et/ou Ti et/ou V et/ou Nb et/ou Ta et/ou La et/ou cérium.
- Utilisation de l'alliage selon l'une des revendications 1 à 23, dans lequel Hf est partiellement remplacé par (en % en poids) 0,01 à 0,1 % d'au moins un des éléments Sc et/ou Ti et/ou V et/ou Nb et/ou Ta et/ou La et/ou cérium.
- Utilisation de l'alliage selon l'une des revendications 1 à 25, comprenant (en % en poids) max. 0,02 % de N et max. 0,005 % de S.
- Utilisation de l'alliage selon l'une des revendications 1 à 26, comprenant (en % en poids) max. 0,01 % de N et max. 0,003 % de S.
- Utilisation de l'alliage selon l'une des revendications 1 à 27, comprenant en outre (en % en poids) max. 0,5 % de nickel, max. 0,1 % de Mo et/ou 0,1 % de W.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 pour l'emploi en tant que feuille dans des éléments de chauffage à chauffer électriquement.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 pour l'emploi en tant que feuille dans des conducteurs chauffants ayant une épaisseur comprise entre 20 et 200 µm.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 pour l'emploi en tant que feuille dans des conducteurs chauffants ayant une épaisseur comprise entre 20 et 100 µm.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 en tant que feuille de conducteur chauffant pour l'emploi dans des plaques cuisson, notamment des plaques cuisson en vitrocéramique.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 en tant que feuille porteuse dans des catalyseurs de gaz d'échappement métalliques et à chauffer.
- Utilisation de l'alliage selon l'une des revendications 1 à 28 en tant que feuille dans des piles à combustible.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL08706758T PL2127472T3 (pl) | 2007-01-29 | 2008-01-15 | Zastosowanie stopu żelazo-chrom-aluminium o dużej trwałości i niewielkiej zmianie oporu cieplnego |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102007005154A DE102007005154B4 (de) | 2007-01-29 | 2007-01-29 | Verwendung einer Eisen-Chrom-Aluminium-Legierung mit hoher Lebensdauer und geringen Änderungen im Warmwiderstand |
PCT/DE2008/000061 WO2008092420A2 (fr) | 2007-01-29 | 2008-01-15 | Utilisation d'un alliage fer-chrome-aluminium ayant une durée de vie élevée et des variations faibles de résistance à la chaleur |
Publications (2)
Publication Number | Publication Date |
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EP2127472A2 EP2127472A2 (fr) | 2009-12-02 |
EP2127472B1 true EP2127472B1 (fr) | 2012-06-27 |
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EP08706758A Active EP2127472B1 (fr) | 2007-01-29 | 2008-01-15 | Utilisation d'un alliage fer-chrome-aluminium ayant une durée de vie élevée et des variations faibles de résistance à la chaleur |
Country Status (8)
Country | Link |
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US (1) | US20100092749A1 (fr) |
EP (1) | EP2127472B1 (fr) |
JP (1) | JP5409390B2 (fr) |
CN (1) | CN101578911B (fr) |
DE (1) | DE102007005154B4 (fr) |
ES (1) | ES2388583T3 (fr) |
PL (1) | PL2127472T3 (fr) |
WO (1) | WO2008092420A2 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US20100092759A1 (en) * | 2008-10-13 | 2010-04-15 | Hua Fan | Fluoropolymer/particulate filled protective sheet |
CN102760508B (zh) * | 2012-07-18 | 2014-05-28 | 中南大学 | 含Hf和Ce的高电导率抗蠕变铝合金电缆导体及制备方法 |
US9777357B2 (en) | 2012-12-17 | 2017-10-03 | Jfe Steel Corporation | Stainless steel foil |
KR101446688B1 (ko) * | 2013-04-11 | 2014-10-07 | (주)칩타시너지코리아 | 고온에서의 내구성 및 내부식성을 보유한 철-크롬-알루미늄 함금, 및 상기 합금으로 제조된 와이어 및 극세사 금속섬유 |
WO2018091727A1 (fr) * | 2016-11-21 | 2018-05-24 | Plastic Omnium Advanced Innovation And Research | Dispositif de chauffage d'un reservoir contenant un liquide corrosif |
CN107805688B (zh) * | 2017-11-03 | 2019-07-02 | 北京首钢吉泰安新材料有限公司 | 一种控制铁铬铝合金细丝米电阻波动范围的方法 |
TWI641001B (zh) * | 2018-01-22 | 2018-11-11 | 國立屏東科技大學 | 薄膜電阻合金 |
US10883160B2 (en) | 2018-02-23 | 2021-01-05 | Ut-Battelle, Llc | Corrosion and creep resistant high Cr FeCrAl alloys |
CN109680206B (zh) * | 2019-03-08 | 2020-10-27 | 北京首钢吉泰安新材料有限公司 | 一种耐高温铁铬铝合金及其制备方法 |
CN113802052A (zh) * | 2020-06-16 | 2021-12-17 | 全球能源互联网研究院有限公司 | 一种含Er元素的Fe-Cr-Al电热合金材料 |
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US4277374A (en) | 1980-01-28 | 1981-07-07 | Allegheny Ludlum Steel Corporation | Ferritic stainless steel substrate for catalytic system |
US4414023A (en) | 1982-04-12 | 1983-11-08 | Allegheny Ludlum Steel Corporation | Iron-chromium-aluminum alloy and article and method therefor |
DE3378099D1 (en) * | 1982-06-24 | 1988-10-27 | Matsushita Electric Ind Co Ltd | Panel heater |
DE3627668C1 (de) * | 1986-08-14 | 1988-03-24 | Thyssen Stahl Ag | Gut schweissbaren Baustahl mit hoher Bestaendigkeit gegen Spannungsrisskorrosion |
DE3706415A1 (de) * | 1987-02-27 | 1988-09-08 | Thyssen Edelstahlwerke Ag | Halbfertigerzeugnis aus ferritischem stahl und seine verwendung |
DE3908526A1 (de) | 1989-03-16 | 1990-09-20 | Vdm Nickel Tech | Ferritische stahllegierung |
EP0516097B1 (fr) * | 1991-05-29 | 1996-08-28 | Kawasaki Steel Corporation | Alliage fer-chrome-aluminium, substrat de catalyseur utilisant cet alliage et le procédé pour sa fabrication |
JPH06116652A (ja) * | 1992-06-30 | 1994-04-26 | Kawasaki Steel Corp | 耐酸化性に優れたFe−Cr−Al薄鋼板の製造方法 |
CN1058363C (zh) * | 1996-04-12 | 2000-11-08 | 杨春益 | 一种电阻率稳定的高温电热材料 |
JPH11130405A (ja) * | 1997-10-28 | 1999-05-18 | Ngk Insulators Ltd | 改質反応装置、触媒装置、それらに用いる発熱・触媒体、及び改質反応装置の運転方法 |
DE19928842C2 (de) | 1999-06-24 | 2001-07-12 | Krupp Vdm Gmbh | Ferritische Legierung |
SE513989C2 (sv) * | 2000-01-01 | 2000-12-11 | Sandvik Ab | Förfarande för tillverkning av ett FeCrAl-material och ett sådant marerial |
JP3350499B2 (ja) * | 2000-01-20 | 2002-11-25 | 新日本製鐵株式会社 | 波付加工性の良い粗面仕上金属箔及び排ガス浄化用触媒担体 |
DE10002933C1 (de) | 2000-01-25 | 2001-07-05 | Krupp Vdm Gmbh | Verfahren zur Herstellung einer formstabilen Eisen-Chrom-Aluminium-Folie sowie Verwendung derselben |
SE517894C2 (sv) * | 2000-09-04 | 2002-07-30 | Sandvik Ab | FeCrAl-legering |
US6485025B1 (en) * | 2000-11-27 | 2002-11-26 | Neomet Limited | Metallic cellular structure |
DE10157749B4 (de) * | 2001-04-26 | 2004-05-27 | Thyssenkrupp Vdm Gmbh | Eisen-Chrom-Aluminium-Legierung |
JP3690325B2 (ja) * | 2001-07-26 | 2005-08-31 | Jfeスチール株式会社 | 耐酸化特性及び耐高温変形性に優れたFe−Cr−Al系合金箔及びその製造方法 |
DE10233624B4 (de) * | 2001-07-27 | 2004-05-13 | Jfe Steel Corp. | Stranggießverfahren für einen Stahl mit hohem Cr- und Al-Gehalt |
DE10310865B3 (de) * | 2003-03-11 | 2004-05-27 | Thyssenkrupp Vdm Gmbh | Eisen-Chrom-Aluminium-Legierung |
DE102005016722A1 (de) * | 2004-04-28 | 2006-02-09 | Thyssenkrupp Vdm Gmbh | Eisen-Chrom-Aluminium-Legierung |
DE102008018135B4 (de) * | 2008-04-10 | 2011-05-19 | Thyssenkrupp Vdm Gmbh | Eisen-Chrom-Aluminium-Legierung mit hoher Lebensdauer und geringen Änderungen im Warmwiderstand |
-
2007
- 2007-01-29 DE DE102007005154A patent/DE102007005154B4/de not_active Expired - Fee Related
-
2008
- 2008-01-15 ES ES08706758T patent/ES2388583T3/es active Active
- 2008-01-15 PL PL08706758T patent/PL2127472T3/pl unknown
- 2008-01-15 US US12/449,127 patent/US20100092749A1/en not_active Abandoned
- 2008-01-15 CN CN2008800013733A patent/CN101578911B/zh active Active
- 2008-01-15 EP EP08706758A patent/EP2127472B1/fr active Active
- 2008-01-15 JP JP2009547523A patent/JP5409390B2/ja active Active
- 2008-01-15 WO PCT/DE2008/000061 patent/WO2008092420A2/fr active Application Filing
Also Published As
Publication number | Publication date |
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PL2127472T3 (pl) | 2012-11-30 |
DE102007005154B4 (de) | 2009-04-09 |
DE102007005154A1 (de) | 2008-07-31 |
ES2388583T3 (es) | 2012-10-16 |
JP5409390B2 (ja) | 2014-02-05 |
CN101578911B (zh) | 2013-07-10 |
EP2127472A2 (fr) | 2009-12-02 |
WO2008092420A2 (fr) | 2008-08-07 |
US20100092749A1 (en) | 2010-04-15 |
WO2008092420A3 (fr) | 2008-09-25 |
JP2010516903A (ja) | 2010-05-20 |
CN101578911A (zh) | 2009-11-11 |
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