EP1573079B1 - Iron alloy, especially for use in an exhaust gas cleaning unit - Google Patents
Iron alloy, especially for use in an exhaust gas cleaning unit Download PDFInfo
- Publication number
- EP1573079B1 EP1573079B1 EP03795900A EP03795900A EP1573079B1 EP 1573079 B1 EP1573079 B1 EP 1573079B1 EP 03795900 A EP03795900 A EP 03795900A EP 03795900 A EP03795900 A EP 03795900A EP 1573079 B1 EP1573079 B1 EP 1573079B1
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- EP
- European Patent Office
- Prior art keywords
- maximally
- ferrous alloy
- exhaust gas
- alloy
- metal film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000004140 cleaning Methods 0.000 title abstract description 7
- 229910000640 Fe alloy Inorganic materials 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract 3
- 229910045601 alloy Inorganic materials 0.000 claims description 37
- 239000000956 alloy Substances 0.000 claims description 37
- 238000000746 purification Methods 0.000 claims description 21
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 14
- 239000002912 waste gas Substances 0.000 claims 4
- 239000005864 Sulphur Substances 0.000 claims 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 2
- 238000003801 milling Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052845 zircon Inorganic materials 0.000 abstract description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000011888 foil Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- -1 iron-chromium-aluminum Chemical compound 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910001029 Hf alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000939 field's metal Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 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
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- 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
- C22C38/06—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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
-
- 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
-
- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Definitions
- the invention relates to an iron alloy, in particular for use for carrier films in an exhaust gas purification unit, a metal foil and an exhaust gas purification unit, in particular an exhaust gas catalyst, particulate filter and mixer, preferably for use in motor vehicles to reduce pollutant emission.
- Known catalyst supports of automotive exhaust gas catalyst systems typically include a ceramic composite body.
- An advantageous alternative to ceramic elements is the use of a metal foil as a metallic Katalysatorhäger in exhaust gas catalyst systems of internal combustion engines. Due to their fast onset, these allow a significantly more efficient reduction of pollutants than ceramic-based catalyst carriers. Furthermore, due to the advantageous physico-technical properties favorable effects on engine performance and pollutant emissions in internal combustion engines.
- US 5,578,265 A discloses an iron alloy for steel foils for catalytic converters which has the following composition (in% by weight): ⁇ 0.02% C, 19-21% Cr, 4.5-6% Al, 0.01-0 , 3% Ce, 0.02-0.05% rare earths, in total, min.
- Mg + Ca 0.015%
- Mg 0.015%
- 0.0005-0.0018% Ca 0.015-0.0018%
- Ca 0.005-0.015%
- La 0.02-0.03% Ce
- P 0.005-0.02%
- S ⁇ 0.5%
- Ni ⁇ 0.1% Mo
- W ⁇ 0.1%
- Co ⁇ 0.1%
- V ⁇ 0.1%
- Co ⁇ 0.1%
- Nn ⁇ 0.1%
- Nb ⁇ 0.1%
- Ti ⁇ 0.015%
- Zr 0.2-0.4%
- Si 0.1 -0.4%
- remainder Fe and impurities 0.015%
- From DE 101 57 749 A is an iron-chromium-aluminum alloy with a long service life, with (in% by mass)> 2-3.6% aluminum and> 10-20% chromium and additions of 0.1-1 % Si, max. 0.5% man, 0.01-0.2% yttrium and / or 0.01-0.2% Hf and / or 0.01-0.3% Zr, max. 0.04% nitrogen, max. 0.04% phosphorus, max. 0.01 & sulfur, max. 0.05% copper and max. 0.01% molybdenum and / or tungsten and the usual manufacturing impurities, remainder iron, which can be used in the form of a film in the field of catalysts.
- WO 01/00896 A1 describes the use of an alloy for producing carrier foils for metallic automotive catalytic converters, which is a ferritic iron-chromium-aluminum-yttrium-hafnium alloy with in (% by weight) the following composition: 22% Cr, 6-10% Al, 0.02-1% Si, max. 0.5% Mn, 0.2-0.1% Hf, 0.02-0.1% Y, max. 0.1% Mg, max. 0.02 96 Ti, max. 0.09% Zr, max. 0.02% rare earth metals, max. 0.1% Fr, max. 0.1% Ca, max. 0.5% Cu, max. 0.1% V, max. 0.1% Ta, max. 0.1% Nb, max. 0.3 96 C, max. 0.01% N, max. 0.01% B, max. 2% Co, max. 2% W, max. 2% Mo, remainder iron as well as melting-related impurities.
- an alloy for producing carrier foils for metallic automotive catalytic converters which is a ferritic iron-chro
- the object of the invention is to adapt the known and proven metal foil carrier concept of catalytic converters in a suitable manner to the needs of truck engines, as well as a metal foil, in particular for use in an exhaust gas purification unit and an exhaust gas purification unit, in particular for use in motor vehicles for reducing to provide the pollutant emission.
- this object is achieved by a carrier foil of an iron alloy with 17-18% by weight of chromium, 0.02-0.05% by weight of carbon, 0.05-0.2% by weight of manganese, 0.1% 0.3 wt.% Silicon, 3.7-4.3 wt.% Aluminum, 0.02-0.04 wt.% Zirconium, max. 0.05 wt.% Titanium, 0.003-0.005 wt.
- % Calcium 0.03-0.05% by weight of vanadium, 0.001-0.01% by weight of tin and rare earth metals in an amount of 0.03-0.07% by weight, and also an iron residue the usual accompanying elements up to an amount of 100 wt .-%, by a metal foil of the alloy according to the invention and by an exhaust gas purification Device with a metal foil made of the alloy according to the invention as a carrier foil dissolved
- Advantageous developments of the abovementioned alloy and of the metal foil are described in the subclaims.
- Emission control units in the sense of the application are basically all components that can be used to purify exhaust gases.
- Exhaust gas purification units are, in particular, catalytic converters, particle filters and mixers which are used in an exhaust system recirculated to an engine to reduce pollutant emission.
- the core of the invention is the consideration to maintain the previous concept of exhaust gas purification units by using a new material for the metal foil.
- the alloy according to the invention is characterized in particular by the fact that it can be used for the cost-effective production of a carrier film. Since the carrier foils produced from the alloy according to the invention also meet all requirements for use on commercial vehicles, their use enables the cost-effective production of compared to catalytic converters for cars constructively unchanged catalytic converters, which are also suitable for use on truck engines Basic, i. complicated and costly changes in the design of the exhaust gas purification units to adapt to the needs of truck engines can be omitted.
- the alloy according to the invention has a high oxidation resistance of more than 1000 ° C. This is achieved by alloying the oxygen-affine elements aluminum and chromium, which under dense atmospheric oxygen, slowly growing, the underneath lying material effectively against corrosion attack protective oxide layers form.
- Aluminum oxide layers generally offer a number of advantages over chromium oxide layers. They grow slower because of the denser packing of the alumina, they do not evaporate, unlike chromium oxide, even at temperatures around 1000 ° C and their protective effect is maintained even under oxygen-poor conditions under which chromium oxides can no longer form.
- the alloying of chromium has the effect of favoring the alumina formation of technical alloys.
- An essential feature of the invention is the alloy of chromium and aluminum with the additions of calcium and rare earth metals.
- the elements zirconium and titanium as well as the rare earth metals improve the behavior under the influence of cyclically changing and long-lasting temperature stress and improve the bond between the oxide layer and the basic matrix.
- These elements, together with chromium and aluminum, further promote the resistance of the protective layers formed during the oxidation.
- high oxygen affinity is essentially characteristic of all the elements mentioned here in low concentrations. This results in a delayed scaling of chromium and aluminum and in addition the adhesion of the oxide layers formed is improved.
- the use of niobium serves to increase strength by acting as a carbide and nitride former.
- the following elements cause the following properties. Chromium and aluminum serve to increase the oxidation resistance. High contents are a prerequisite for a long service life, especially with cyclically occurring temperature loads.
- the zirconium also causes the chromium content to be retained even in the case of thermal stresses in the microstructure in metallic form. Titanium has essentially the same effect, but the Impact on resistance, scaling and mechanical properties at elevated temperatures lower than for zirconium as an additional alloying element.
- the addition of calcium has a positive effect on the oxidation resistance at higher temperatures.
- the alloy has sufficient thermal shock resistance. Furthermore, there is sufficient creep resistance, which prevents undesirable deformation. It can be economically, i. with high output and the lowest possible use of energy by conventional methods melt metallurgical, large-scale manufacture.
- the alloy has sufficient ductility to allow cost-effective cold working to thin metal foils and to wind and further deform these metal foils into support material.
- the alloy is useful for creating a texture on the metal foil during cold forming of the alloy into thin metal foils.
- the texture of the metal foils can be chosen by adjusting the production parameters so that they correspond to a desired body-centered metallic polycrystalline texture development. As a result, the deformability of the metal foils is increased and facilitates their further processing.
- a metal foil of an alloy according to the invention as a carrier film allows the low-cost production of an exhaust gas purification unit due to the low cost of producing the alloy and due to the low cost of further processing into a carrier film, so that large-volume exhaust gas catalysts for truck engines can be produced economically.
- the use of a metal foil of the alloy according to the invention as a carrier film prevents the occurrence of so-called "breakaway corrosion" even after longer run times of the exhaust gas purification unit, ie the spalling of the protective oxide layers due to the exponential increase of the corrosion layer thickness as a result of depletion of a Covering layer forming element is reliably prevented.
- a significant delay of the "breakaway corosion" is thereby provided by the provision of the cover layer forming element in a sufficient, an annealing destroyed cover layers enabling quantity achieved.
- the exhaust gas purification unit according to the invention is further distinguished by its long service life resulting from the longevity of the metal foil produced from the alloy according to the invention.
- the vote and composition of the alloy contents is chosen so that, despite a low film thickness and the resulting limited reservoir of aluminum for annealing the destroyed layers safe cold and hot forming of the material is possible.
- Such exhaust gas cleaning units are suitable for installation in motor vehicles of all kinds and there allows a significant reduction in pollutant emissions.
- the exhaust gas cleaning unit according to the invention is suitable for installation both in front of and behind a possibly existing exhaust gas turbocharger.
- the exhaust gas cleaning unit meets the increased requirements for vibration resistance.
- the high thermal shock and thermal shock resistance of the metal foils produced from the alloy according to the invention is sufficient to withstand the severe temperature changes on the catalytic converter occurring when starting and stopping the engine.
- the creep resistance of the alloy prevents unacceptable deformation of the catalytic converter, which causes cracking of the oxide layers and the occurrence of breakaway corrosion could be promoted.
- the exhaust gas purification unit according to the invention by the use of a metal foil according to the invention has a higher cell count, so that up to reaching the necessary operating temperature of the exhaust gas cleaning unit pollutants can be cached in higher amounts.
- the metal foil has a thickness of at least 15 ⁇ m.
- Exhaust gas purification unit made using such thin metal foils has increased vibration resistance in contrast to corresponding ceramic-based exhaust gas purification units.
- the cell number of the exhaust gas purification unit can be further increased and thus the buffer volume for pollutants can be further increased.
- such trained exhaust purification unit faster the necessary operating temperature, so that the pollutant emission can be further reduced.
- a ceramic coating which is applied to the honeycomb-shaped metal foils, can be effectively and environmentally friendly separated from the metal foils.
- the valuable precious metals are deposited in high concentration in the then separated coating.
- the high-alloy metal foils can also be recycled.
- Figure 1 shows the schematic structure of an exhaust unit 1, which is integrated in operation on a motor vehicle in an exhaust system, not shown here.
- the exhaust unit is formed by a plurality of metal foils 3, which are arranged intertwined in a cylindrical housing 2.
- the metal foils 3 extending in the catalytic converter 1, starting from the housing wall involute in the direction of the central axis of the cylindrical housing 2, each with alternating direction of curvature about three arranged around the central axis of the housing 2 reversal lines 4a, 4b, 4c.
- the metal foils 3 are connected to the housing 2 by brazing.
Abstract
Description
Die Erfindung betrifft eine Eisenlegierung, insbesondere zur Verwendung für Trägerfolien in einer Abgasreinigungseinheit, eine Metallfolie sowie eine Abgasreinigungseinheit, insbesondere einen Abgaskatalysator, Partikelfilter und Mischer, vorzugsweise zum Einsatz in Kraftfahrzeugen zur Reduzierung der Schadstoffemission.The invention relates to an iron alloy, in particular for use for carrier films in an exhaust gas purification unit, a metal foil and an exhaust gas purification unit, in particular an exhaust gas catalyst, particulate filter and mixer, preferably for use in motor vehicles to reduce pollutant emission.
Bekannte Katalysatorträger von Abgaskatalysatorsystemen von Automobilen weisen üblicherweise einen keramischen Verbundkörper auf. Eine vorteilhafte Alternative zu keramischen Elementen bildet die Verwendung einer Metallfolie als metallischer Katalysatorhäger in Abgaskatalysatorsystemen von Verbrennungsmotoren. Diese ermöglichen wegen ihres schnellen Anspringens eine deutlich effizientere Schadstoffreduzierung als Katalysatorträger auf Keramikbasis. Ferner bestehen aufgrund der vorteilhaften physikalisch-technischen Eigenschaften günstige Auswirkungen auf die Motorleistung und die Schadstoffemission bei Verbrennungsmotoren.Known catalyst supports of automotive exhaust gas catalyst systems typically include a ceramic composite body. An advantageous alternative to ceramic elements is the use of a metal foil as a metallic Katalysatorhäger in exhaust gas catalyst systems of internal combustion engines. Due to their fast onset, these allow a significantly more efficient reduction of pollutants than ceramic-based catalyst carriers. Furthermore, due to the advantageous physico-technical properties favorable effects on engine performance and pollutant emissions in internal combustion engines.
Die aus dem PKW-Bereich bekannten metallischen Träger und Trägermaterialien für Katalysatoren können zwar grundsätzlich auch für LKW-Katalysatoren verwendet werden, bei einem Materialbedarf von ca. 500g des Trägermaterials pro Liter Motorvdumen des LKW-Motors für einen LKW-Katalysator ergibt sich jedoch ein erhöhter Materialbedarf an Trägermaterial für einen einzelnen LKW-Katalysator. Aufgrund der hohen Matenalkosten des bekannten Trägermaterials ist deshalb eine Herstellung eines LKW-Katalysators auf metallischer Basis nicht wirtschaftlich.Although the known from the automotive field metal support and support materials for catalysts can in principle be used for truck catalysts, with a material requirement of about 500g of the carrier material per liter of engine capacity of the truck engine for a truck catalyst, however, results in an increased Material requirement for carrier material for a single truck catalytic converter. Because of the high material cost of the known support material, therefore, production of a metallic-based truck catalyst is not economical.
Gesteigerte Anforderungen resultieren auch aus dem Einsatzbereich des Katalysators. So muß dieser zur Anordnung vor oder hinter einem Turbolader geeignet sein. Erhöhte Anforderungen bestehen auch an die Thermoschock- und Temperaturwechselfestigkeit sowie an die Vibrations- und Oxidationsbeständigkeit.Increased requirements also result from the application of the catalyst. So this must be suitable for arrangement in front of or behind a turbocharger. There are also increased demands on the thermal shock and thermal shock resistance as well as on the resistance to vibration and oxidation.
Die US 5,578,265 A offenbart eine Eisenlegierung für Stahlfolien für Abgaskatalysatoren, die folgende Zusammensetzung hat (in Gew.-%): ≤ 0,02 % C, 19-21 % Cr, 4,5-6 % Al, 0,01-0,3 % Ce, 0,02-0,05 % seltene Erden, insgesamt, mind. 0,015 % Mg+Ca, und optional 0,015-0,025 % Mg, 0,0005-0,0018 % Ca, 0,005-0,015 % La, 0,02-0,03 % Ce, und außerdem optional 0,005-0,02 % P, ≤ 0,005 % S, ≤ 0,5 % Ni, ≤ 0,1 % Mo, ≤ 0,1 % W, ≤ 0,1 % Co, ≤ 0,1 % V, ≤ 0,1 % Co, ≤ 0,1 % Nn, ≤ 0,1 % Nb, ≤ 0,1 % N, ≤ 0,015 % Ti, ≤ 0,015% Zr, 0,2-0,4 % Mn, 0,1-0,4 % Si, Rest Fe und Verunreinigungen. Aus der DE 101 57 749 A ist eine Eisen-Chrom-Aluminium-Legierung mit hoher Lebensdauer, mit (in Massen-%) > 2-3,6 % Aluminium und > 10-20 % Chrom sowie Zugaben von 0,1-1 % Si, max. 0,5 % Man, 0,01-0,2 % Yttrium und/oder 0,01-0,2 % Hf und/oder 0,01-0,3 % Zr, max. 0,04 % Stickstoff, max. 0,04 % Phosphor, max. 0,01 & Schwefel, max. 0,05 % Kupfer und jeweils max. 0,01 % Molybdän und/oder Wolfram sowie den üblichen herstellungsbedingten Verunreinigungen, Rest Eisen bekannt, welche in Form einer Folie auf dem Gebiet der Katalysatoren eingesetzt werden kann.US 5,578,265 A discloses an iron alloy for steel foils for catalytic converters which has the following composition (in% by weight): ≤ 0.02% C, 19-21% Cr, 4.5-6% Al, 0.01-0 , 3% Ce, 0.02-0.05% rare earths, in total, min. 0.015% Mg + Ca, and optionally 0.015-0.025% Mg, 0.0005-0.0018% Ca, 0.005-0.015% La, 0.02-0.03% Ce, and also optional 0.005-0.02% P, ≤ 0.005% S, ≤ 0.5% Ni, ≤ 0.1% Mo, ≤ 0.1% W, ≤ 0.1% Co, ≤ 0.1% V, ≤ 0.1% Co, ≤ 0.1% Nn, ≤ 0.1% Nb, ≤ 0.1% N, ≤ 0.015% Ti, ≤ 0.015% Zr, 0.2-0.4% Mn, 0.1 -0.4% Si, remainder Fe and impurities. From DE 101 57 749 A is an iron-chromium-aluminum alloy with a long service life, with (in% by mass)> 2-3.6% aluminum and> 10-20% chromium and additions of 0.1-1 % Si, max. 0.5% man, 0.01-0.2% yttrium and / or 0.01-0.2% Hf and / or 0.01-0.3% Zr, max. 0.04% nitrogen, max. 0.04% phosphorus, max. 0.01 & sulfur, max. 0.05% copper and max. 0.01% molybdenum and / or tungsten and the usual manufacturing impurities, remainder iron, which can be used in the form of a film in the field of catalysts.
Die W0 01/00896 A1 beschreibt die Verwendung einer Legierung zum Herstellen von Trägerfolien für metallische Automobil Abgaskatalysatoren, wobei es sich um eine feritische Eisen-Chrom-Aluminium-Yttrium-Hafnium-Legierung mit in (Gew.-%) folgender Zusammensetzung: 16-22 % Cr, 6-10 % Al, 0,02-1 % Si, max. 0,5 % Mn, 0,2-0,1 % Hf, 0,02-0,1 % Y, max. 0,1 % Mg, max. 0,02 96 Ti, max. 0,09 % Zr, max. 0,02 % seltene Erdmetalle, max. 0,1 % Fr, max. 0,1 % Ca, max. 0,5 % Cu, max. 0,1 % V, max. 0,1 % Ta, max. 0,1 % Nb, max. 0,3 96 C, max. 0,01 % N, max. 0,01 % B, max. 2 % Co, max. 2 % W, max. 2 % Mo, Rest Eisen sowie erschmelzungsbedingte Verunreinigungen handelt.WO 01/00896 A1 describes the use of an alloy for producing carrier foils for metallic automotive catalytic converters, which is a ferritic iron-chromium-aluminum-yttrium-hafnium alloy with in (% by weight) the following composition: 22% Cr, 6-10% Al, 0.02-1% Si, max. 0.5% Mn, 0.2-0.1% Hf, 0.02-0.1% Y, max. 0.1% Mg, max. 0.02 96 Ti, max. 0.09% Zr, max. 0.02% rare earth metals, max. 0.1% Fr, max. 0.1% Ca, max. 0.5% Cu, max. 0.1% V, max. 0.1% Ta, max. 0.1% Nb, max. 0.3 96 C, max. 0.01% N, max. 0.01% B, max. 2% Co, max. 2% W, max. 2% Mo, remainder iron as well as melting-related impurities.
Der Erfindung liegt die Aufgabe zu Grund, das von PKW Verbrennungsmotoren bekannte und bewährte Metallfolienträgerkonzept der Abgaskatalysatoren in geeigneter Weise an die Bedürfnisse von LKW Motoren anzupassen, sowie eine Metallfolie, insbesondere zur Verwendung in einer Abgasreinigungseinheit und eine Abgasreinigungseinheit, insbesondere zum Einsatz in Kraftfahrzeugen zur Verringerung der Schadstoffemission bereitzustellen.The object of the invention is to adapt the known and proven metal foil carrier concept of catalytic converters in a suitable manner to the needs of truck engines, as well as a metal foil, in particular for use in an exhaust gas purification unit and an exhaust gas purification unit, in particular for use in motor vehicles for reducing to provide the pollutant emission.
Erfindungsgemäß wird diese Aufgabe durch eine Trägerfolie aus einer Eisenlegierung mit 17-18 Gew.-% Chrom, 0,02-0,05 Gew.-% Kohlenstoff, 0,05-0,2 Gew.-% Mangan, 0,1-0,3 Gew.-% Silizium, 3,7-4,3 Gew.-% Aluminium, 0,02-0,04 Gew.-% Zirkon, maximal 0,05 Gew.-% Titan, 0,003-0,005 Gew.-% Kalzium, 0,03-0,05 Gew.-% Vanadium, 0,001-0,01 Gew.-% Zinn und Seltene Erdmetalle in einer Menge von 0,03-0,07 Gew.-% sowie einen Rest Eisen mit den üblichen Begleitelementen bis auf eine Menge von 100 Gew.-%, durch eine Metallfolie aus der erfindungsgemäßen Legierung sowie durch eine Abgasreinigungs einheit mit einer Metallfolie aus der erfindungsgemäßen Legierung als Trägerfolie gelöst Vorteilhafte Weiterbildungen der vorgenannten Legierung und der Metallfolie sind in den Unteransprüchen beschrieben.According to the invention, this object is achieved by a carrier foil of an iron alloy with 17-18% by weight of chromium, 0.02-0.05% by weight of carbon, 0.05-0.2% by weight of manganese, 0.1% 0.3 wt.% Silicon, 3.7-4.3 wt.% Aluminum, 0.02-0.04 wt.% Zirconium, max. 0.05 wt.% Titanium, 0.003-0.005 wt. % Calcium, 0.03-0.05% by weight of vanadium, 0.001-0.01% by weight of tin and rare earth metals in an amount of 0.03-0.07% by weight, and also an iron residue the usual accompanying elements up to an amount of 100 wt .-%, by a metal foil of the alloy according to the invention and by an exhaust gas purification Device with a metal foil made of the alloy according to the invention as a carrier foil dissolved Advantageous developments of the abovementioned alloy and of the metal foil are described in the subclaims.
Abgasreinigungseinheiten im Sinne der Anmeldung sind grundsätzlich alle Komponenten, die zur Reinigung von Abgasen eingesetzt werden können. Abgasreinigungseinheiten sind insbesondere Abgaskatalysatoren, Partikelfilter und Mischer, die in einer einem Motor nachgelegten Abgasanlage zur Reduzierung der Schadstoffemission eingesetzt werden.Emission control units in the sense of the application are basically all components that can be used to purify exhaust gases. Exhaust gas purification units are, in particular, catalytic converters, particle filters and mixers which are used in an exhaust system recirculated to an engine to reduce pollutant emission.
Kern der Erfindung ist die Überlegung, die bisherige Konzeption von Abgasreinigungseinheiten durch Verwendung eines neuen Werkstoffs für die Metallfolie beizubehalten. Die erfindungsgemäße Legierung zeichnet sich insbesondere dadurch aus, daß sie zur kostengünstigen Herstellung einer Trägerfolie verwendet werden kann. Da die aus der erfindungsgemäßen Legierung hergestellten Trägerfolien zudem alle Anforderungen an den Einsatz an Nutzfahrzeugen erfüllen, ermöglicht deren Verwendung die kostengünstige Herstellung von gegenüber Abgaskatalysatoren für PKWs konstruktiv unveränderten Abgaskatalysatoren, die auch für den Einsatz an LKW Motoren geeignet sind Grundlegende, d.h. komplizierte und kostenintensive Änderungen des konstruktiven Aufbaus der Abgasreinigungseinheiten zur Anpassung an die Bedürfnisse von LKW Motoren können unterbleiben.The core of the invention is the consideration to maintain the previous concept of exhaust gas purification units by using a new material for the metal foil. The alloy according to the invention is characterized in particular by the fact that it can be used for the cost-effective production of a carrier film. Since the carrier foils produced from the alloy according to the invention also meet all requirements for use on commercial vehicles, their use enables the cost-effective production of compared to catalytic converters for cars constructively unchanged catalytic converters, which are also suitable for use on truck engines Basic, i. complicated and costly changes in the design of the exhaust gas purification units to adapt to the needs of truck engines can be omitted.
Die erfindungsgemäße Legierung weist eine hohe Oxidationsbeständigkeit von mehr als 1000°C auf. Dies wird durch das Zulegieren der sauerstoffaffinen Elemente Aluminium sowie Chrom erreicht, welche unter Luftsauerstoff dichte, langsam wachsende, das darunter liegende Material effektiv gegen Korrosionsangriff schützende Oxidschichten ausbilden. Dabei bieten Aluminiumoxidschichten gegenüber Chromoxidschichten generell eine Reihe von Vorteilen. Sie wachsen wegen der dichteren Packung des Aluminiumoxids langsamer, sie dampfen, anders als Chromoxid, auch bei Temperaturen um 1000°C nicht ab und ihre Schutzwirkung bleibt auch unter sauerstoffarmen Bedingungen erhalten, unter denen sich Chromoxide nicht mehr bilden können. Das Zulegieren von Chrom hat den Effekt, daß die Aluminiumoxidbildung technischer Legierungen begünstigt wird.The alloy according to the invention has a high oxidation resistance of more than 1000 ° C. This is achieved by alloying the oxygen-affine elements aluminum and chromium, which under dense atmospheric oxygen, slowly growing, the underneath lying material effectively against corrosion attack protective oxide layers form. Aluminum oxide layers generally offer a number of advantages over chromium oxide layers. They grow slower because of the denser packing of the alumina, they do not evaporate, unlike chromium oxide, even at temperatures around 1000 ° C and their protective effect is maintained even under oxygen-poor conditions under which chromium oxides can no longer form. The alloying of chromium has the effect of favoring the alumina formation of technical alloys.
Wesentliches Merkmal der Erfindung ist die Legierung aus Chrom und Aluminium mit den Zusätzen aus Kalzium und Seltenen Erdmetallen. Die Elemente Zirkon und Titan sowie die Seltenen Erdmetalle verbessern das Verhalten unter dem Einfluß zyklisch wechselnder sowie langanhaltender Temperaturbelastung und verbessern den Verbund zwischen Oxidschicht und Grundmatrix. Diese Elemente fördern ferner gemeinsam mit Chrom und Aluminium die Beständigkeit der während der Oxidation entstehenden Schutzschichten. Neben der Verbesserung der Werkstoffeigenschaften ist im wesentlichen für alle hier genannten Elemente in geringen Konzentrationen eine hohe Sauerstoffaffinität charakteristisch. Daraus resultiert eine verzögerte Verzunderung von Chrom und Aluminium und zusätzlich wird das Haftvermögen der gebildeten Oxidschichten verbessert. Die Verwendung von Niob dient zur Steigerung der Festigkeit, indem es als Karbid- und Nitridbildner fungiert.An essential feature of the invention is the alloy of chromium and aluminum with the additions of calcium and rare earth metals. The elements zirconium and titanium as well as the rare earth metals improve the behavior under the influence of cyclically changing and long-lasting temperature stress and improve the bond between the oxide layer and the basic matrix. These elements, together with chromium and aluminum, further promote the resistance of the protective layers formed during the oxidation. In addition to the improvement of the material properties, high oxygen affinity is essentially characteristic of all the elements mentioned here in low concentrations. This results in a delayed scaling of chromium and aluminum and in addition the adhesion of the oxide layers formed is improved. The use of niobium serves to increase strength by acting as a carbide and nitride former.
Durch die Zusätze von mehreren sauerstoffaffinen Elementen in Kombination sowie von Seltenen Erdmetallen ergibt sich ferner eine hitzebeständige Stahllegierung für erhöhte Anwendungstemperaturen. Die Legierung bildet bei erhöhten Temperaturen auch bei wechselnder Belastung eine festhaftende Aluminiumoxidschicht. Die Legierungselemente erhöhen zudem die Duktilität und die Formstabilität der aus der Legierung hergestellten Metallfolien auch in einem Temperaturbereich oberhalb von 1000°C.The addition of several oxygen-affinity elements in combination and of rare earth metals also results in a heat-resistant steel alloy for increased application temperatures. At elevated temperatures, the alloy forms a firmly adhering aluminum oxide layer even under alternating load. In addition, the alloying elements increase the ductility and the dimensional stability of the metal foils produced from the alloy even in a temperature range above 1000 ° C.
In den aus der erfindungsgemäßen Legierung hergestellten Metallfolien bewirken die folgenden Elemente folgende Eigenschaften. Chrom und Aluminium dienen zur Erhöhung des Oxidationswiderstandes. Hohe Gehalte sind Voraussetzung für eine lange Lebensdauer vor allem bei zyklisch auftretenden Temperaturbelastungen. Das Zirkon bewirkt zudem, daß der Chromanteil auch bei thermischen Belastungen in der Mikrostruktur in metallischer Form erhalten bleibt. Titan hat im wesentlichen den gleichen Effekt, jedoch sind die Auswirkungen auf das Widerstandsverhalten, die Zunderbeständigkeit sowie die mechanischen Eigenschaften bei erhöhten Temperaturen geringer als bei Zirkon als zusätzlichem Legierungselement. Der Zusatz von Kalcium hat eine positive Auswirkung auf die Oxidationsbeständigkeit bei höheren Temperaturen.In the metal foils prepared from the alloy of the present invention, the following elements cause the following properties. Chromium and aluminum serve to increase the oxidation resistance. High contents are a prerequisite for a long service life, especially with cyclically occurring temperature loads. The zirconium also causes the chromium content to be retained even in the case of thermal stresses in the microstructure in metallic form. Titanium has essentially the same effect, but the Impact on resistance, scaling and mechanical properties at elevated temperatures lower than for zirconium as an additional alloying element. The addition of calcium has a positive effect on the oxidation resistance at higher temperatures.
Die Legierung weist eine ausreichende Thermoschockbeständigkeit auf. Ferner besteht eine ausreichende Kriechfestigkeit, die eine unerwünschte Verformung verhindert. Sie läßt sich wirtschaftlich, d.h. mit hoher Ausbringung und möglichst geringem Einsatz an Energie mit konventionellen Verfahren schmelzmetallurgisch, großtechnisch herstellen. Die Legierung weist eine ausreichende Duktilität auf, um eine kostengünstige Kaltverformung zu dünnen Metallfolien und das Aufwickeln und weiteres Verformen dieser Metallfolien zu Trägermaterial zu ermöglichen.The alloy has sufficient thermal shock resistance. Furthermore, there is sufficient creep resistance, which prevents undesirable deformation. It can be economically, i. with high output and the lowest possible use of energy by conventional methods melt metallurgical, large-scale manufacture. The alloy has sufficient ductility to allow cost-effective cold working to thin metal foils and to wind and further deform these metal foils into support material.
Zudem eignet sich die Legierung zum Erzeugen einer Textur auf der Metallfolie während einer Kaltverformung der Legierung zu dünnen Metallfolien. Die Textur der Metallfolien kann dabei durch Einstellen der Produktions-Parameter so gewählt werden, daß sie einer gewünschten raumzentrierten metallischen polykristallinen Texturentwicklung entspricht. Hierdurch wird die Verformbarkeit der Metallfolien erhöht und deren Weiterverarbeitung erleichtert.In addition, the alloy is useful for creating a texture on the metal foil during cold forming of the alloy into thin metal foils. The texture of the metal foils can be chosen by adjusting the production parameters so that they correspond to a desired body-centered metallic polycrystalline texture development. As a result, the deformability of the metal foils is increased and facilitates their further processing.
Die Verwendung einer Metallfolie aus einer erfindungsgemäßen Legierung als Trägerfolie ermöglicht aufgrund der geringen Kosten für die Herstellung der Legierung sowie aufgrund der geringen Kosten bei der Weiterverarbeitung zu einer Trägerfolie die kostengünstige Herstellung einer Abgasreinigungseinheit, so daß auch großvolumige Abgaskatalysatoren für LKW Motoren wirtschaftlich hergestellt werden können.The use of a metal foil of an alloy according to the invention as a carrier film allows the low-cost production of an exhaust gas purification unit due to the low cost of producing the alloy and due to the low cost of further processing into a carrier film, so that large-volume exhaust gas catalysts for truck engines can be produced economically.
In einer erfindungsgemäßen Abgasreinigungseinheit verhindert die Verwendung einer Metallfolie aus der erfindungsgemäßen Legierung als Trägerfolie auch nach längeren Laufzeiten der Abgasreinigungseinheit das Auftreten einer sogenannten "breakaway corrosion", d.h. das Abplatzen der schützenden Oxidschichten aufgrund des mit der Zeit exponentiellen Anstiegs der Korrosionsschichtdicke in Folge einer Verarmung eines deckschichtbildenden Elements wird zuverlässig verhindert. Eine deutliche Verzögerung der "breakaway corosion" wird dabei durch das Zurverfügungstellen des die Deckschicht bildenden Elements in einer ausreichenden, eine Ausheilung zerstörter Deckschichten ermöglichenden Menge erreicht.In an exhaust gas purification unit according to the invention, the use of a metal foil of the alloy according to the invention as a carrier film prevents the occurrence of so-called "breakaway corrosion" even after longer run times of the exhaust gas purification unit, ie the spalling of the protective oxide layers due to the exponential increase of the corrosion layer thickness as a result of depletion of a Covering layer forming element is reliably prevented. A significant delay of the "breakaway corosion" is thereby provided by the provision of the cover layer forming element in a sufficient, an annealing destroyed cover layers enabling quantity achieved.
Die erfindungsgemäße Abgasreinigungseinheit zeichnet sich ferner durch ihre hohe Lebensdauer aus, die aus der Langlebigkeit der aus der erfindungsgemäßen Legierung hergestellten Metallfolie resultiert. Die Abstimmung und Zusammensetzung der Legierungsinhalte ist dabei so gewählt, daß trotz einer geringen Foliendicke und des daraus nur begrenzten Reservoirs an Aluminium zum Ausheilen der zerstörten Schichten eine sichere Kalt- und Warmformgebung des Werkstoffs möglich ist.The exhaust gas purification unit according to the invention is further distinguished by its long service life resulting from the longevity of the metal foil produced from the alloy according to the invention. The vote and composition of the alloy contents is chosen so that, despite a low film thickness and the resulting limited reservoir of aluminum for annealing the destroyed layers safe cold and hot forming of the material is possible.
Derartige Abgasreinigungseinheiten eignen sich zum Einbau in Kraftfahrzeuge aller Art und ermöglicht dort eine deutliche Verringerung der Schadstoffemissionen.Such exhaust gas cleaning units are suitable for installation in motor vehicles of all kinds and there allows a significant reduction in pollutant emissions.
Ferner eignet sich die erfindungsgemäße Abgasreinigungseinheit zum Einbau sowohl vor als auch hinter einem ggf. vorhandenen Abgasturbolader. Die Abgasreinigungseinheit erfüllt die erhöhten Anforderungen an die Vibrationsbeständigkeit. Die hohe Thermoschock- und Temperaturwechselfestigkeit der aus der erfindungsgemäßen Legierung hergestellten Metallfolien reicht aus, um die beim Anlassen und Abstellen des Motors auftretenden starken Temperaturwechsel am Abgaskatalysator auszuhalten. Die Kriechfestigkeit der Legierung verhindert eine unzulässige Verformung des Abgaskatalysators, wodurch ein Aufreißen der Oxidschichten bewirkt und das Auftreten der "breakaway corrosion" begünstigt werden könnte.Furthermore, the exhaust gas cleaning unit according to the invention is suitable for installation both in front of and behind a possibly existing exhaust gas turbocharger. The exhaust gas cleaning unit meets the increased requirements for vibration resistance. The high thermal shock and thermal shock resistance of the metal foils produced from the alloy according to the invention is sufficient to withstand the severe temperature changes on the catalytic converter occurring when starting and stopping the engine. The creep resistance of the alloy prevents unacceptable deformation of the catalytic converter, which causes cracking of the oxide layers and the occurrence of breakaway corrosion could be promoted.
Gegenüber Abgaskatalysatoren auf Keramikbasis weist die erfindungsgemäße Abgasreinigungseinheit durch die Verwendung einer erfindungsgemäßen Metallfolie eine höhere Zellenzahl auf, so daß bis zum Erreichen der notwendigen Betriebstemperatur der Abgasreinigungseinheit Schadstoffe in höheren Mengen zwischengespeichert werden können.Compared with catalytic converters based on ceramics, the exhaust gas purification unit according to the invention by the use of a metal foil according to the invention has a higher cell count, so that up to reaching the necessary operating temperature of the exhaust gas cleaning unit pollutants can be cached in higher amounts.
Nach einer vorteilhaften Weiterbildung der Erfindung weist die Metallfolie eine Dicke von mindestens 15 µm auf. Abgasreinigungseinheit, die unter Verwendung derart dünner Metallfolien hergestellt wurden, weisen im Gegensatz zu entsprechenden Abgasreinigungseinheiten auf Keramikbasis eine erhöhte Vibrationsbeständigkeit auf. Ferner kann durch die Verwendung derartiger Metallfolien in einer Abgasreinigungseinheit die Zellenzahl der Abgasreinigungseinheit weiter erhöht und somit das Zwischenspeichervolumen für Schadstoffe weiter gesteigert werden. Zudem erreichen derart ausgebildete Abgasreinigungseinheit schneller die notwendige Betriebstemperatur, so daß die Schadstoffemission weiter reduziert werden kann.According to an advantageous development of the invention, the metal foil has a thickness of at least 15 μm. Exhaust gas purification unit made using such thin metal foils has increased vibration resistance in contrast to corresponding ceramic-based exhaust gas purification units. Furthermore, by using such metal foils in an exhaust gas purification unit, the cell number of the exhaust gas purification unit can be further increased and thus the buffer volume for pollutants can be further increased. In addition, such trained exhaust purification unit faster the necessary operating temperature, so that the pollutant emission can be further reduced.
Abgenutzte Abgasreinigunseinheiten der erfindungsgemäßen Art können nahezu vollständig der Wiederverwendung zugefügt werden. Eine keramische Beschichtung, welche auf die zu Waben geformten Metallfolien aufgebracht ist, kann effektiv und umweltschonend von den Metallfolien getrennt werden. Dabei fallen die wertvollen Edelmetalle in hoher Konzentration in der dann separierten Beschichtung an. Auch die hochlegierten Metallfolien können dem Recycling zugeführt werden.Worn Abgasreinigunseinheiten the type of the invention can be almost completely added to the reuse. A ceramic coating, which is applied to the honeycomb-shaped metal foils, can be effectively and environmentally friendly separated from the metal foils. The valuable precious metals are deposited in high concentration in the then separated coating. The high-alloy metal foils can also be recycled.
Ein Ausführungsbeispiel der Erfindung wird nachstehend mit Bezug auf die Zeichnung näher erläutert.An embodiment of the invention will be explained below with reference to the drawing.
Figur 1 zeigt den schematischen Aufbau einer Abgaseinheit 1, der im Betrieb an einem Kraftfahrzeug in eine hier nicht dargestellte Abgasanlage integriert ist. Die Abgaseinheit wird durch mehrere Metallfolien 3 gebildet, die ineinander verschlungen in einem zylindrischen Gehäuse 2 angeordnet sind.Figure 1 shows the schematic structure of an
Nach schmelzmetallurgischer Herstellung der Legierung bestehend aus 17,5 Gew.-% Chrom, 0,03 Gew.-% Kohlenstoff, 0,1 Gew.-% Mangan, 0,2 Gew.-% Silizium, 3,9 Gew.-% Aluminium,0,03 Gew.-% Zirkon, 0,03 Gew.-% Titan, 0,001 Gew.-% Phosphor, 0,001 Gew.-% Schwefel, 0,004 Gew.-% Kalzium, 0,008 Gew.-% Niob, 0,04 Gew.-% Vanadium,0,005 Gew.-% Zinn, 0,1 Gew.-% Nickel, 0,005 Gew.-% Magnesium, 0,005 Gew.-% Stickstoff, 0,04 Gew.-% Kupfer, 0,005 Gew.-% Blei, 0,03 Gew.-% Molybdän, Seltenen Erdmetallen in einer Menge von 0,05 Gew.-% und Eisen mit den üblichen Begleitelementen wurde diese als Strang abgegossen. Durch Kaltwalzen wurde die Legierung anschließend zu den Metallfolien 3 verarbeitet, die in der Abgaseinheit 1 eingesetzt werden und eine Dicke von mindestens 15 µm aufweisen.After melt-metallurgical production of the alloy consisting of 17.5% by weight of chromium, 0.03% by weight of carbon, 0.1% by weight of manganese, 0.2% by weight of silicon, 3.9% by weight Aluminum, 0.03 wt% zircon, 0.03 wt% titanium, 0.001 wt% phosphorus, 0.001 wt% sulfur, 0.004 wt% calcium, 0.008 wt% niobium, 0, 04% by weight vanadium, 0.005% by weight tin, 0.1% by weight nickel, 0.005% by weight magnesium, 0.005% by weight nitrogen, 0.04% by weight copper, 0.005% by weight % Lead, 0.03 wt .-% molybdenum, rare earth metals in an amount of 0.05 wt .-% and iron with the usual accompanying elements, this was poured off as a strand. By cold rolling, the alloy was then processed into the metal foils 3, which are used in the
Die Metallfolien 3 erstrecken sich im Abgaskatalysator 1 ausgehend von der Gehäusewand evolventenförmig in Richtung auf die Mittelachse des zylinderförmigen Gehäuses 2 mit jeweils abwechselnder Krümmungsrichtung um drei um die Mittelachse des Gehäuses 2 angeordnete Umkehrlinien 4a, 4b, 4c. An der Innenwand des Gehäuses 2 sind die Metallfolien 3 durch Hartlöten mit dem Gehäuse 2 verbunden.The metal foils 3 extending in the
Claims (17)
- A ferrous alloy, in particular for use as a backing film, characterized in that it contains- 17-18 wt% chromium,- 0,02-0,05 wt% carbon,- 0,05-0,2 wt% manganese,- 0,1-0,3 wt% silicon,- 3,7-4,3 wt% aluminium,- 0,02-0,04 wt% zirconium,- maximally 0,05 wt% titanium,- 0,003-0,005 wt% calcium,- 0,03-0,05 wt% vanadium,- 0,001-0,01 wt% tin and- rare earth metals at a quantity of 0,03-0,07 wt%, preferably lanthanum at a quantity of 0,006-0,04 wt%, as well as a ferrous balance including normal impurities up to a quantity of 100 wt%.
- A ferrous alloy, as claimed in claim 1, in particular for use as a backing film, characterized in that it contains- 17-18 wt% chromium,- 0,02-0,05 wt% carbon,- maximally 0,2 wt% manganese,- maximally 0,3 wt% silicon,- 3,7-4,3 wt% aluminium,- 0,02-0,04 wt% zirconium,- maximally 0,05 wt% titanium,- 0,003-0,005 wt% calcium,- 0,03-0,05 wt% vanadium,- maximally 0,01 wt% tin,- rare earth metals at a quantity of 0,03-0,07 wt%, and alternately- one or several of the following elements:- nickel of maximally 0,5 wt%,- magnesium of maximally 0,01 wt%,- nitrogen of 0,001-0,01 wt%,- copper of 0,001-0,07 wt%,- niobium of 0,001-0,02 wt%,- phosphorus of 0,001-0,025 wt%,- sulphur of maximally 0,003 wt%,- molybdenum of maximally 0,1 wt% and- lead of maximally 0,015 wt% as well as- a ferrous balance including normal impurities up to a quantity of 100 wt%.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,15 wt% nickel.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,007 wt% magnesium.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,0075 wt% nitrogen.
- A ferrous alloy as claimed in claim 2, characterized in that it contains 0,03-0,05 wt% copper.
- A ferrous alloy as claimed in claim 2, characterized in that it contains 0,006-0,01 wt% niobium.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,015 wt% phosphorus.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,002 wt% sulphur.
- A ferrous alloy as claimed in claim 1 or claim 2, characterized in that the rare earth metals comprise lanthanum at a quantity of 0,006-0,04 wt%, preferably 0,008-0,03 wt%.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,08 wt% molybdenum.
- A ferrous alloy as claimed in claim 2, characterized in that it contains maximally 0,01 wt% lead.
- A metal film, in particular for use in a waste gas purification unit, characterized in that it is manufactured from an alloy according to one or several of claims 1 to 12.
- A metal film as claimed in claim 13, characterized in that it has a texture adjustable with regard to milling aspects.
- A metal film as claimed in claim 13 or claim 14, characterized in that the texture is formed such that the metal film shows high formability.
- A metal film as claimed in one or several of claims 13 to 15, characterized in that it has a thickness of at least 15 µm.
- A waste gas purification unit, in particular a waste gas catalytic converter, a particle filter or a mixer for use in motor vehicles for reducing pollutant emission, characterized in that the waste gas purification unit (1) includes a metal film (3) according to one or several of claims 13 to 16, as a backing film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI200330470T SI1573079T1 (en) | 2002-12-20 | 2003-12-16 | Iron alloy, especially for use in an exhaust gas cleaning unit |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10261207A DE10261207A1 (en) | 2002-12-20 | 2002-12-20 | Iron alloy, in particular for use in an exhaust gas cleaning unit |
| DE10261207 | 2002-12-20 | ||
| PCT/EP2003/014355 WO2004059025A1 (en) | 2002-12-20 | 2003-12-16 | Iron alloy, especially for use in an exhaust gas cleaning unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1573079A1 EP1573079A1 (en) | 2005-09-14 |
| EP1573079B1 true EP1573079B1 (en) | 2006-07-26 |
Family
ID=32519408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03795900A Expired - Lifetime EP1573079B1 (en) | 2002-12-20 | 2003-12-16 | Iron alloy, especially for use in an exhaust gas cleaning unit |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1573079B1 (en) |
| AT (1) | ATE334233T1 (en) |
| AU (1) | AU2003298189A1 (en) |
| DE (2) | DE10261207A1 (en) |
| WO (1) | WO2004059025A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH441773A (en) * | 1960-06-13 | 1967-08-15 | Du Pont | Dispersion alloy |
| GB1568091A (en) * | 1976-05-13 | 1980-05-21 | Zaidan Hojin Denki Jiki Zairyo | High damping capacity alloy |
| AU600009B2 (en) * | 1986-08-18 | 1990-08-02 | Inco Alloys International Inc. | Dispersion strengthened alloy |
| JPH04147945A (en) * | 1990-10-11 | 1992-05-21 | Nisshin Steel Co Ltd | High al-containing ferritic stainless steel excellent in high temperature oxidation resistance and toughness |
| US5578265A (en) * | 1992-09-08 | 1996-11-26 | Sandvik Ab | Ferritic stainless steel alloy for use as catalytic converter material |
| DE19928842C2 (en) * | 1999-06-24 | 2001-07-12 | Krupp Vdm Gmbh | Ferritic alloy |
| DE10157749B4 (en) * | 2001-04-26 | 2004-05-27 | Thyssenkrupp Vdm Gmbh | Iron-chromium-aluminum alloy |
-
2002
- 2002-12-20 DE DE10261207A patent/DE10261207A1/en not_active Withdrawn
-
2003
- 2003-12-16 WO PCT/EP2003/014355 patent/WO2004059025A1/en not_active Application Discontinuation
- 2003-12-16 AU AU2003298189A patent/AU2003298189A1/en not_active Abandoned
- 2003-12-16 DE DE50304398T patent/DE50304398D1/en not_active Expired - Lifetime
- 2003-12-16 EP EP03795900A patent/EP1573079B1/en not_active Expired - Lifetime
- 2003-12-16 AT AT03795900T patent/ATE334233T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1573079A1 (en) | 2005-09-14 |
| DE50304398D1 (en) | 2006-09-07 |
| WO2004059025A1 (en) | 2004-07-15 |
| DE10261207A1 (en) | 2004-07-15 |
| AU2003298189A1 (en) | 2004-07-22 |
| ATE334233T1 (en) | 2006-08-15 |
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