EP1752561A1 - Article protected against high temperature corrosion and reciprocating pistion internal combustion engine or turbine or combustion unit containing the article - Google Patents
Article protected against high temperature corrosion and reciprocating pistion internal combustion engine or turbine or combustion unit containing the article Download PDFInfo
- Publication number
- EP1752561A1 EP1752561A1 EP06405297A EP06405297A EP1752561A1 EP 1752561 A1 EP1752561 A1 EP 1752561A1 EP 06405297 A EP06405297 A EP 06405297A EP 06405297 A EP06405297 A EP 06405297A EP 1752561 A1 EP1752561 A1 EP 1752561A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- workpiece
- elements
- weight percent
- vanadium
- component
- Prior art date
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Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 46
- 238000005260 corrosion Methods 0.000 title claims abstract description 46
- 238000002485 combustion reaction Methods 0.000 title claims description 52
- 238000002844 melting Methods 0.000 claims abstract description 58
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002344 surface layer Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000004056 waste incineration Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 238000005275 alloying Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 239000000446 fuel Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/286—Particular treatment of blades, e.g. to increase durability or resistance against corrosion or erosion
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/288—Protective coatings for blades
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/02—Surface coverings of combustion-gas-swept parts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/48—Preventing corrosion
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
- F23M5/00—Casings; Linings; Walls
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
- F23R3/002—Wall structures
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2220/00—Application
- F05D2220/40—Application in turbochargers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2230/00—Manufacture
- F05D2230/90—Coating; Surface treatment
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
- F23M2900/00—Special features of, or arrangements for combustion chambers
- F23M2900/05004—Special materials for walls or lining
Definitions
- the invention relates to a workpiece with protection against high-temperature corrosion by melting phases, e.g. low-melting Vanadatphasen, a reciprocating internal combustion engine, in particular two-stroke large diesel engine, an incinerator and a use for protection against high temperature corrosion according to the preamble of the independent claim of the respective category.
- melting phases e.g. low-melting Vanadatphasen
- a reciprocating internal combustion engine in particular two-stroke large diesel engine
- an incinerator an incinerator and a use for protection against high temperature corrosion according to the preamble of the independent claim of the respective category.
- Protective coatings against high temperature corrosion are well known in the art.
- surface protective layers which offer high resistance to corrosion, in particular to oxidation or sulfidation at high temperatures and in chemically aggressive environments. They are produced, for example, by thermal spraying, with MCrAlY layers being widely used as high-temperature corrosion protection.
- the metal M may, for example, iron, cobalt or nickel or an alloy of these or others Be metals.
- Aluminum-chromium layers, which are formed for example by Chromalit Schl show in many applications, a more or less good resistance to high-temperature corrosion, especially in sulfate-containing media.
- the phenomenon of high-temperature corrosion can occur wherever relatively high process temperatures of several 100 ° C to well over 1000 ° C prevail, often not only the high temperatures are responsible as such for the occurrence of corrosive effects, but also to meet chemically aggressive environmental conditions for example, due to combustion products or other chemical reaction products, or may be caused by additions to fuels, lubricants, etc.
- combustion plants for example the components of a combustion chamber of a waste incineration plant, or of course the components of a combustion chamber of a land- or air-supported turbine, especially the turbine blades, the walls of the combustion chamber, the Fuel injection systems and exhaust systems of turbines.
- the expert of course a variety of other workpieces are known, which are threatened as components of various devices of high temperature corrosion.
- molten phases may contain vanadates, especially for the combustion of heavy oil, such as, for example, sodium vanadylvanadates, which are detectable by X-ray, among other things.
- the melting that is, the occurrence of the molten, eg vanadium phases contained from about 400 ° C can be observed.
- molten phases are capable of chemically decomposing protective oxide layers grown on a metal, so that the underlying metal is vulnerable to attack by high-temperature corrosion.
- the entrainment of the necessary alloying elements with the lubricating oil and / or the fuel or fuel is not readily possible in all cases, since the alloying elements can enter into physical and / or chemical reactions with the lubricating oil and / or the fuel or fuel, for example lead that the corresponding alloying element is then no longer available for the formation of, for example, the high-melting vanadates available. It is also possible that by the aforementioned physical and / or chemical reactions certain properties, such as the lubricating oil, are changed so much that the lubricating oil, for example, completely or partially loses its lubricating effect, resulting in significant damage to a corresponding machine can.
- the materials from which, for example, a known surface coating is applied relatively expensive because they consist on the one hand of a variety of relatively expensive basic substances and on the other hand, the production, such as in the case of thermal spraying, relatively expensive.
- the known protective layers always optimized with respect to certain corrosion processes, so that ultimately a certain surface protection layer always represents a compromise, so that although the high-temperature corrosion is minimized, it is ultimately not prevented to the necessary extent.
- the known surface layers are often not resistant to deep-melting phases and are dissolved or detached from them, for example, or have a certain permeability, for example for the low-melting vanadates, so that they have their corrosive effect on the workpiece, eg on a piston of a Internal combustion engine, despite surface protection layer can develop.
- the invention thus relates to a workpiece with protection against high-temperature corrosion by deep-melting vanadate phases, wherein the workpiece has at least one surface layer on one surface which is one of the elements consisting of the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co, so that in the operating state by a chemical reaction between an element consisting of the Group of elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co and the vanadium present and / or the vanadium compounds present and / or a vanadium low melting phase, a high melting Vanadatphase is formed, so that the Formation of a low-melting vanadate phase is preventable.
- the edge layer can be an edge layer of the workpiece itself, in which the previously enumerated elements have been introduced in the desired concentration and composition, or the edge layer can be applied to a base body according to one of the techniques described below, wherein the main body itself from a other material or may be formed from the same material.
- Essential to the invention is thus that is not prevented by the formation of a surface layer primarily the contact of the harmful deep-melting phases with the surface of the workpiece. But it is already the formation of harmful substances that lead to high-temperature corrosion, thereby preventing that a conversion of, for example, low-melting vanadium phases in high-melting vanadates or the formation of low-melting vanadates is prevented from the outset by directly the formation of high-melting vanadates, bypassing the formation of low-melting vanadates is preferred.
- the alloying elements introduced into the base material of the workpiece susceptible to corrosion react with the combustion products such that no deep-melting phases are formed, but only high-melting phases which do not melt at a typical operating temperature in the combustion chamber and therefore do not know those of molten phases Can cause corrosion damage.
- the high-temperature corrosion protection according to the present invention has proved to be so efficient that the high-temperature corrosion protection against deep-melting phases over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high temperatures of 900 ° C, about 1200 ° C. and even up to over 1400 ° C, under a variety of operating conditions and in very different chemical environments, guaranteed.
- the high-temperature corrosion protection according to the invention is not only suitable for protecting workpieces, such as the parts of a large diesel engine, but can be used to advantage in all areas of technology, in which workpieces, such as components or machine components of high-temperature corrosion due to deep-melting phases, even under aggressive chemical Boundary conditions and difficult temperature conditions are threatened.
- one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co. is provided at least in an edge layer of a surface of the tool. It has been found that these elements are very effective, that is with high yield and high reaction rate, sufficiently high melting phases, e.g. Vanadates form, if they are provided in a predetermined concentration, which may be dependent inter alia on the base material of the workpiece, and / or may be determined by the combustion temperature or the operating temperature of the workpiece.
- the concentration and / or the mixing ratio of the abovementioned alloying elements, or which of the abovementioned alloying elements are advantageously used or not used may also depend on boundary conditions other than those mentioned above. For example, among other things, the nature and quality of the fuel or fuel used, the type and quality of any lubricant used or other combustion additive and many other operating parameters under which the workpiece is operated in the operating condition.
- a surface layer is provided on the surface of a workpiece according to the invention, which is in particular soldered, welded, mechanically bonded, applied by melting technology, hot-isostatically pressed or sprayed on, in particular thermally sprayed, the surface layer of one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co.
- This is particularly advantageous when the workpiece, for example, is exposed to mechanical wear on the surface and the surface must be renewed from time to time in a repair process.
- a new surface layer can be applied so that the surface of the workpiece is not only restored mechanically, ie structurally, but the newly prepared surface layer also again in sufficient concentration on the aforementioned alloying elements, so that the formation of deep-melting phases is further reliably prevented even after repair of the surface.
- the surface layer may consist of impurities of pure Co or of pure Ni.
- the proportion of each of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si is between 1% by weight and 80% by weight, preferably between 2% by weight and 70% by weight and / or the proportion of Co and / or Ni is preferably between 1% and 99% by weight, in particular when using iron-based materials.
- the workpiece as a whole may consist of an alloy comprising one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe and Co.
- This is particularly advantageous if during operation, for example, a surface of the workpiece with time is damaged or more or less removed, a repair of the workpiece due to its function still need not be provided. In such a case, the formation of the deep-melting phases can be ensured without sacrificing the efficiency even if, for example, the surface of the workpiece is worn or damaged in operation over time.
- nickel, nickel-cobalt and / or cobalt-based alloys are then also suitable as base alloys.
- the proportion of each of the elements Co and Ni is between 1% and 50% by weight, in particular between 2% and 35% by weight, which may in certain cases prevent various mechanical properties of the material , such as its hardness, toughness, yield strength, thermal expansion coefficient, etc. deteriorate. In particular, this can be counteracted by embrittlement of the material.
- the workpiece is in particular, but not necessarily, a component of a combustion system of an internal combustion engine, in particular a two-stroke large diesel engine, preferably a piston, a piston ring, a gas exchange valve, an injection nozzle, a component inserted or mounted in a combustion chamber a combustion chamber forming component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or an exhaust gas inlet or outlet.
- a component of a combustion system of an internal combustion engine in particular a two-stroke large diesel engine
- the workpiece may be a component of a turbine, in particular a combustion chamber or a turbine blade of a gas turbine, or a component of an incinerator, in particular a waste incineration plant, in particular a component of a combustion chamber or an exhaust system of a combustion plant.
- the invention relates to a reciprocating internal combustion engine, in particular a two-stroke large diesel engine, a turbine or an incinerator, in particular a waste incineration plant with a workpiece of the type described above with a protection against high-temperature corrosion by deep-melting phases.
- the invention further relates to the use of at least one of the group of elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co for protecting a workpiece against High-temperature corrosion by deep-melting vanadate phases, the workpiece having on one surface at least one boundary layer comprising one of the elements consisting of the group of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co, such that in the operating state by a chemical reaction between an element consisting of the group of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co and the vanadium present and / or the vanadium compounds present and / or a low-melting vanadate phase, a high-melting vanadate phase is formed, so that the formation of a low-melting vanadate phase is prevented.
- a surface layer is used on the surface of the workpiece, in particular soldered, welded, mechanically bonded, applied by melting, hot isostatically pressed or sprayed, in particular thermally sprayed, wherein in the surface layer of one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co are provided.
- a surface layer is used which, except for impurities, consists of pure Co or of pure Ni.
- the workpiece itself is made of an alloy comprising one of the elements of the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe and Co.
- a chemical composition wherein the proportion of each of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si is between 1% weight percent and 50%. Percent by weight, preferably between 2% and 35% by weight, especially when a Co, Fe, or Ni base alloy is used for the workpiece.
- the workpiece is a component of a combustion system of an internal combustion engine, in particular a two-stroke large diesel engine, preferably a piston, a piston ring, a gas exchange valve, an injection nozzle, a combustion chamber forming component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or an exhaust gas inlet or outlet.
- a combustion system of an internal combustion engine in particular a two-stroke large diesel engine
- the workpiece is a component of a turbine, in particular a combustion chamber or a turbine blade of a gas turbine, or a component of an incinerator, in particular a waste incineration plant, in particular a component of a combustion chamber or an exhaust system of an incinerator.
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Abstract
Description
Die Erfindung betrifft ein Werkstück mit einem Schutz gegen Hochtemperaturkorrosion durch schmelzende Phasen, z.B. tiefschmelzende Vanadatphasen, eine Hubkolbenbrennkraftmaschine, insbesondere Zweitakt-Grossdieselmotor, eine Verbrennungsanlage und eine Verwendung zum Schutz gegen Hochtemperaturkorrosion gemäss dem Oberbegriff des unabhängigen Anspruchs der jeweiligen Kategorie.The invention relates to a workpiece with protection against high-temperature corrosion by melting phases, e.g. low-melting Vanadatphasen, a reciprocating internal combustion engine, in particular two-stroke large diesel engine, an incinerator and a use for protection against high temperature corrosion according to the preamble of the independent claim of the respective category.
Schutzschichten gegen Hochtemperaturkorrosion, häufig auch einfach als Heisskorrosion oder Heissgaskorrosion bezeichnet, sind im Stand der Technik wohlbekannt. Man versteht darunter zum Beispiel Oberflächenschutzschichten, die einen hohen Widerstand gegen Korrosion, insbesondere gegen Oxidation oder Sulfidation bei hohen Temperaturen und in chemisch aggressiven Umgebungen bieten. Sie werden beispielsweise durch thermisches Spritzen hergestellt, wobei MCrAIY-Schichten als Hochtemperaturkorrosionsschutz weit verbreitet sind. Das Metall M kann dabei z.B. Eisen, Kobalt oder Nickel oder eine Legierung dieser oder anderer Metalle sein. Auch Aluminium-Chrom-Schichten, die zum Beispiel durch Chromalitieren gebildet werden, zeigen in vielen Anwendungen eine mehr oder weniger gute Beständigkeit gegen Hochtemperaturkorrosion, insbesondere in sulfathaltigen Medien.Protective coatings against high temperature corrosion, often referred to simply as hot corrosion or hot gas corrosion, are well known in the art. For example, it is understood to mean surface protective layers which offer high resistance to corrosion, in particular to oxidation or sulfidation at high temperatures and in chemically aggressive environments. They are produced, for example, by thermal spraying, with MCrAlY layers being widely used as high-temperature corrosion protection. The metal M may, for example, iron, cobalt or nickel or an alloy of these or others Be metals. Aluminum-chromium layers, which are formed for example by Chromalitieren show in many applications, a more or less good resistance to high-temperature corrosion, especially in sulfate-containing media.
Das Phänomen der Hochtemperaturkorrosion kann dabei überall dort auftreten, wo relativ hohe Prozesstemperaturen von einigen 100°C bis weit über 1000°C herrschen, wobei häufig nicht nur die hohen Temperaturen als solches für das Auftreten korrosiver Effekte verantwortlich sind, sondern auch chemisch aggressive Umgebungsbedingungen anzutreffen sind, die zum Beispiel auf Verbrennungsprodukte oder andere chemische Reaktionsprodukte zurückzuführen sind oder auch von Beimischungen in Brennstoffen, Schmiermitteln usw. hervorgerufen werden können.The phenomenon of high-temperature corrosion can occur wherever relatively high process temperatures of several 100 ° C to well over 1000 ° C prevail, often not only the high temperatures are responsible as such for the occurrence of corrosive effects, but also to meet chemically aggressive environmental conditions for example, due to combustion products or other chemical reaction products, or may be caused by additions to fuels, lubricants, etc.
Somit sind besonders Werkstücke, Bauteile und Maschinenkomponenten, die in mehr oder weniger direktem Kontakt mit Verbrennungsvorgängen stehen, von Hochtemperaturkorrosion bedroht. Beispiele hierfür sind Kolbenoberflächen von Kolben in Brennkraftmaschinen, Zylinderwände, Zylinderdeckel, Einspritzdüsen, Gaswechselventile, aber auch die Komponenten der Abgassysteme von Brennkraftmaschinen, wie zum Beispiel Turbolader, insbesondere auch Turbinenteile und / oder die Abgas Zu- oder Abführung von Abgas- und Turbolader-Systemen. In der
Weitere Beispiele sind die Komponenten von Verbrennungsanlagen, beispielsweise die Komponenten eines Brennraums einer Müllverbrennungsanlage, oder natürlich auch die Komponenten eines Brennraums einer land- oder luftgestützten Turbine, vor allem die Turbinenschaufeln, die Wände der Brennkammer, die Treibstoffeinspritzsysteme und die Abgassysteme von Turbinen. Darüber hinaus sind dem Fachmann selbstverständlich eine Vielzahl anderer Werkstücke bekannt, die als Komponenten verschiedenster Einrichtungen von Hochtemperaturkorrosion bedroht sind.Further examples are the components of combustion plants, for example the components of a combustion chamber of a waste incineration plant, or of course the components of a combustion chamber of a land- or air-supported turbine, especially the turbine blades, the walls of the combustion chamber, the Fuel injection systems and exhaust systems of turbines. In addition, the expert of course a variety of other workpieces are known, which are threatened as components of various devices of high temperature corrosion.
Exemplarisch sollen im folgenden kurz Probleme in Bezug auf Hochtemperaturkorrosion erläutert werden, wie sie beim Betrieb von Grossdieselmotoren, aber nicht nur bei diesen, seit langem bekannt sind und bisher nicht in befriedigender Weise gelöst werden konnten.By way of example, problems relating to high-temperature corrosion are briefly explained below, as they have long been known in the operation of large diesel engines, but not only in these, and so far could not be solved in a satisfactory manner.
Ein wesentlicher Einfluss der in einer Verbrennungsmaschine, insbesondere in einem Grossdieselmotor zu beobachtenden Hochtemperaturkorrosion geht von schmelzflüssigen Phasen aus. Solche schmelzflüssigen Phasen können vor allem bei Verbrennung von Schweröl Vanadate enthalten, wie zum Beispiel Natriumvanadylvanadate, die unter anderem röntgenographisch nachweisbar sind.An essential influence of the high-temperature corrosion to be observed in an internal combustion engine, in particular in a large diesel engine, is based on molten phases. Such molten phases may contain vanadates, especially for the combustion of heavy oil, such as, for example, sodium vanadylvanadates, which are detectable by X-ray, among other things.
Technische Hintergrundinformationen zu Vanadat induzierten Korrosionsprozessen findet man zum Beispiel in dem Artikel von
Beim Betrieb eines Dieselmotors kann die Aufschmelzung, das heisst das Auftreten der schmelzflüssigen, z.B. Vanadium enthaltenen Phasen ab ca. 400°C beobachtet werden. Solche schmelzflüssigen Phasen sind unter anderem in der Lage, quasi natürlich auf einem Metall aufgewachsene schützende Oxidschichten chemisch aufzuschliessen, so dass das darunter liegende Metall schutzlos einem Angriff durch Hochtemperaturkorrosion ausgeliefert ist. In der Veröffentlichung "
Dabei ist es bekannt, dass die Bildung tief schmelzender Vanadatphasen durch Zugabe von bestimmten Legierungselementen verhinderbar ist, da die zuvor genannten Legierungselemente die Ausbildung hochschmelzender Vanadiumphasen ausbilden, die dann bei den im Verbrennungsraum im Betriebszustand herrschenden Temperaturen nicht aufschmelzen, also im wesentlichen nicht aufgeschmolzene Aschen bilden, wodurch der Schutz gegen Hochtemperaturkorrosion entschieden verbessert ist.It is known that the formation of deep melting Vanadatphasen by adding certain alloying elements can be prevented, since the aforementioned alloying elements form the formation of refractory vanadium phases, which then do not melt at the temperatures prevailing in the combustion chamber in the operating temperature, so do not form substantially melted ashes , whereby the protection against high-temperature corrosion is decidedly improved.
Zur Zuführung der zuvor genannten bestimmten Legierungselemente zur Bildung der hoch schmelzenden Phasen, z.B. in den Brennraum einer Brennkraftmaschine, wird bei den aus dem Stand der Technik bekannten Lösungen vorgeschlagen, die notwendigen Legierungselemente zur Bildung der hoch schmelzenden Phasen entweder über das Schmierölsystem oder direkt über das Kraftstoffsystem der Verbrennung im Verbrennungsraum zuzuführen, um die Bildung tief schmelzender, Vanadium enthaltende Phasen zu verhindern. Die Zuführung von Additiven zur Bekämpfung von Korrosions- und Ablagerungserscheinungen ist auch aus anderen technischen Gebieten bekannt. So wird eine solche Massnahme z.B. in "
Diese aus dem Stand der Technik bekannten Möglichkeiten der Zumischung geeigneter Legierungselemente haben jedoch verschiedene erhebliche Nachteile, und haben in Bezug auf bestimmte Legierungen oder Legierungselemente, die zur Bildung der hoch schmelzenden Phase einem Verbrennungsprozess zugeführt werden müssen, lediglich theoretischen Charakter.These known from the prior art ways of admixing suitable alloying elements, however, have several significant disadvantages, and have in relation to certain alloys or alloying elements, the formation of the high-melting phase Combustion process must be fed, only theoretical character.
So müssen Einrichtungen vorgesehen werden, mit welchen gezielt einem Brennstoff, einem Treibstoff oder einem Schmiermittel geeignete Legierungselemente zugeführt werden können, da diese in den Schmierölen bzw. Brenn- und Treibstoffen nicht in der erforderlichen Menge und / oder Zusammensetzung vorhanden sind. Es versteht sich, dass das mit einem ganz erheblichen zusätzlichen apparativen Aufwand verbunden ist, der insbesondere beispielsweise auf Schiffen unter verfahrenstechnischen und wirtschaftlichen Gesichtspunkten, oder einfach aus Platzgründen kaum vernünftig realisierbar ist.Thus, facilities must be provided with which targeted a fuel, a fuel or a lubricant suitable alloying elements can be supplied, since these are not present in the lubricating oils or fuels in the required amount and / or composition. It is understood that this is associated with a very considerable additional expenditure on equipment, which is in particular, for example, on ships under procedural and economic aspects, or just for reasons of space hardly reasonably feasible.
Zudem ist die Mitführung der notwendigen Legierungselemente mit dem Schmieröl und / oder dem Treibstoff oder Brennstoff nicht in allen Fällen ohne weiteres möglich, da die Legierungselemente z.B. mit dem Schmieröl und / oder dem Treibstoff oder Brennstoff physikalische und / oder chemische Reaktionen eingehen können, die dazu führen, dass das entsprechende Legierungselement dann nicht mehr zur Bildung z.B. der hoch schmelzenden Vanadate zur Verfügung steht. Auch ist es möglich, dass durch die zuvor erwähnten physikalischen und / oder chemischen Reaktionen bestimmte Eigenschaften, z.B. des Schmieröls, so stark verändert werden, dass das Schmieröl zum Beispiel seine schmierende Wirkung ganz oder teilweise verliert, was zu erheblichen Schäden an einer entsprechenden Maschine führen kann. Auch ist es möglich, dass sich durch die Zumischung der Legierungselemente zum Treibstoff und / oder zum Schmieröl physikalisch und / oder chemisch aggressive Stoffe bilden können, die bestimmte Maschinenelemente angreifen und massiv beschädigen können, bevor die Legierungselemente ihre Wirkung zur Bildung hoch schmelzender Vanadiumverbindungen entfalten können.In addition, the entrainment of the necessary alloying elements with the lubricating oil and / or the fuel or fuel is not readily possible in all cases, since the alloying elements can enter into physical and / or chemical reactions with the lubricating oil and / or the fuel or fuel, for example lead that the corresponding alloying element is then no longer available for the formation of, for example, the high-melting vanadates available. It is also possible that by the aforementioned physical and / or chemical reactions certain properties, such as the lubricating oil, are changed so much that the lubricating oil, for example, completely or partially loses its lubricating effect, resulting in significant damage to a corresponding machine can. It is also possible that physically and / or chemically aggressive substances can form due to the admixture of the alloying elements to the fuel and / or lubricating oil, which can attack and massively damage certain machine elements before the alloying elements can unfold their effect to form highly melting vanadium compounds ,
Auch wenn die zuvor exemplarisch beschriebenen Probleme mit den tief schmelzenden Vanadat Phasen nur ein Beispiel für einen Mechanismus ist, der zu Hochtemperaturkorrosion führt und dem Fachmann eine Vielzahl weiterer Mechanismen und Hochtemperaturkorrosionseffekte bekannt sind, die ebenfalls, und zwar nicht nur in Dieselmotoren, beobachtet werden, und zum Beispiel in den oben genannten Anlagen und / oder an den genannten Komponenten im Betrieb zu den bekannten Korrosionsschäden führen können, so ist das Problem mit den tief schmelzenden Phasen jedoch ein zentrales Problem, dem bisher kaum Beachtung geschenkt wurde und für dessen Lösung es bisher keine wirklich praktikablen Vorschläge gibt.Although the problems with the deep-melting vanadate phases described above by way of example are only one example of a mechanism which leads to high-temperature corrosion and a variety of other mechanisms and high-temperature corrosion effects are known to those skilled in the art, which are also observed, not only in diesel engines, and, for example, in the above-mentioned plants and / or on the components mentioned in the operation can lead to the known corrosion damage, so the problem with the deep-melting phases, however, is a central problem that has received little attention so far and for the solution it so far There are no really practical suggestions.
Dabei soll nochmals ausdrücklich erwähnt werden, dass das Problem der tief schmelzenden Phasen nicht nur in Verbrennungsmaschinen, insbesondere in Zweitakt-Grossdieselmotoren und anderen kleineren Hubkolbenverbrennungsmaschinen auftritt, sondern auch aus vielen anderen technischen Bereichen bekannt ist, wie zum Beispiel bei Verbrennungsanlagen, insbesondere bei Müllverbrennungsanlagen, oder aber auch bei luft- oder landgestützten Turbinen aller Art.It should again be mentioned explicitly that the problem of deep-melting phases not only in internal combustion engines, especially in two-stroke large diesel engines and other smaller reciprocating internal combustion engines, but is also known from many other technical fields, such as in incinerators, especially in waste incineration plants, or even in air or land-based turbines of all kinds.
Auch wenn, wie bereits eingangs erwähnt, aus dem Stand der Technik verschiedene Massnahmen bekannt sind, um das Auftreten von Hochtemperaturkorrosion zu minimieren, haben die aus dem Stand der Technik bekannten Massnahmen verschiedene Nachteile und sind insbesondere nicht geeignet, das Auftreten der tief schmelzenden Phasen zu verhindern.Even if, as already mentioned, various measures are known from the prior art in order to minimize the occurrence of high-temperature corrosion, the measures known from the prior art have various disadvantages and are in particular unsuitable for the occurrence of the low-melting phases prevent.
Darüber hinaus sind die Materialien, aus denen zum Beispiel eine bekannte Oberflächenbeschichtung aufgebracht wird, relativ teuer, da sie einerseits aus einer Vielzahl verhältnismässig teuerer Grundsubstanzen bestehen und andererseits die Herstellung, wie zum Beispiel im Fall von thermischem Spritzen, relativ aufwendig ist. Auch sind die bekannten Schutzschichten immer in Bezug auf bestimmte Korrosionsprozesse optimiert, so dass eine bestimmte Oberflächenschutzschicht letztlich immer einen Kompromiss darstellt, so dass die Hochtemperaturkorrosion zwar minimiert, aber letztlich nicht im notwendigen Umfang verhindert wird. Vor allem sind die bekannten Oberflächenschichten gegen tief schmelzende Phasen häufig nicht resistent und werden von diesen zum Beispiel aufgelöst oder abgelöst, oder weisen eine bestimmte Durchlässigkeit z.B. für die tief schmelzenden Vanadate auf, so dass diese ihre korrodierende Wirkung am Werkstück, z.B. an einem Kolben einer Brennkraftmaschine, trotz Oberflächenschutzschicht entfalten können.In addition, the materials from which, for example, a known surface coating is applied, relatively expensive because they consist on the one hand of a variety of relatively expensive basic substances and on the other hand, the production, such as in the case of thermal spraying, relatively expensive. Also, the known protective layers always optimized with respect to certain corrosion processes, so that ultimately a certain surface protection layer always represents a compromise, so that although the high-temperature corrosion is minimized, it is ultimately not prevented to the necessary extent. Above all, the known surface layers are often not resistant to deep-melting phases and are dissolved or detached from them, for example, or have a certain permeability, for example for the low-melting vanadates, so that they have their corrosive effect on the workpiece, eg on a piston of a Internal combustion engine, despite surface protection layer can develop.
Es ist somit eine Aufgabe der Erfindung ein verbessertes korrosionsgeschütztes Werkstück für hohe Temperaturen zur Verfügung zu stellen, wobei der Korrosionsschutz durch den Einsatz von einigen wenigen gut verfügbaren Materialien bereitgestellt wird, das korrosionsgeschützte Werkstück somit besonders wirtschaftlich herstellbar ist, und das Werkstück insbesondere gegen Schäden durch Hochtemperaturkorrosionsmechanismen basierend auf tiefschmelzenden Phasen wirksam geschützt ist.It is therefore an object of the invention to provide an improved corrosion-protected workpiece for high temperatures, wherein the corrosion protection is provided by the use of a few readily available materials, the corrosion-protected workpiece is thus particularly economical to produce, and the workpiece in particular against damage High-temperature corrosion mechanisms based on deep-melting phases is effectively protected.
Die diese Aufgaben lösenden Gegenstände der Erfindung sind durch die Merkmale der unabhängigen Ansprüche gekennzeichnet.The objects of the invention solving these objects are characterized by the features of the independent claims.
Die abhängigen Ansprüche beziehen sich auf besonders vorteilhafte Ausführungsformen der Erfindung.The dependent claims relate to particularly advantageous embodiments of the invention.
Die Erfindung betrifft somit ein Werkstück mit einem Schutz gegen Hochtemperaturkorrosion durch tief schmelzende Vanadatphasen wobei das Werkstück an einer Oberfläche mindestens eine Randschicht aufweist, die eines der Elemente bestehend aus der Gruppe der Element Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co umfasst, so dass im Betriebszustand durch eine chemische Reaktion zwischen einem Element bestehend aus der Gruppe der Elemente Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co und dem anwesenden Vanadium und / oder den anwesenden Vanadiumverbindungen und / oder einer tiefschmelzenden Vanadatphase, eine hochschmelzende Vanadatphase bildbar ist, so dass die Bildung einer tiefschmelzenden Vanadatphase verhinderbar ist.The invention thus relates to a workpiece with protection against high-temperature corrosion by deep-melting vanadate phases, wherein the workpiece has at least one surface layer on one surface which is one of the elements consisting of the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co, so that in the operating state by a chemical reaction between an element consisting of the Group of elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co and the vanadium present and / or the vanadium compounds present and / or a vanadium low melting phase, a high melting Vanadatphase is formed, so that the Formation of a low-melting vanadate phase is preventable.
Dabei kann die Randschicht eine Randschicht des Werkstücks selbst sein, in die die zuvor aufgezählten Elemente in der gewünschten Konzentration und Zusammensetzung eingebracht worden sind, oder die Randschicht kann auf einem Grundkörper gemäss einem der weiter unten beschriebenen Techniken aufgebracht werden, wobei der Grundkörper selbst aus einem anderen Material oder auch aus dem gleichen Material gebildet sein kann.In this case, the edge layer can be an edge layer of the workpiece itself, in which the previously enumerated elements have been introduced in the desired concentration and composition, or the edge layer can be applied to a base body according to one of the techniques described below, wherein the main body itself from a other material or may be formed from the same material.
Es hat sich nämlich gezeigt, dass durch Zugabe von geeigneten Legierungselementen zu den Basiswerkstoffen von durch Hochtemperaturkorrosion gefährdeten Komponenten, wie zum Beispiel zum Basiswerkstoff eines Kolbens einer Hubkolbenbrennkraftmaschine, die schädlichen Wirkungen der z.B. bei der Schwerölverbrennung auftretenden, bei tiefen Temperaturen schmelzflüssigen Vanadat Phasen, dadurch verhinderbar sind, dass die derartig mit geeigneten Legierungselementen dotierten Komponenten die Bildung der tief schmelzenden Vanadate zumindest an der Oberfläche des Werkstücks verhinderbar ist, so dass entsprechende Korrosionsschäden durch tief schmelzende Vanadate gar nicht mehr auftreten können.It has been found that by adding suitable alloying elements to the base materials of high-temperature-corrosion-endangered components, such as the base material of a piston of a reciprocating internal combustion engine, the harmful effects of e.g. occurring in the heavy oil combustion, at low temperatures molten vanadate phases, thereby preventable, that the doped with suitable alloying components components, the formation of the low-melting vanadate at least on the surface of the workpiece can be prevented, so that corresponding corrosion damage by deep-melting vanadate no longer may occur.
Wesentlich für die Erfindung ist somit, dass nicht durch die Ausbildung einer Oberflächenschicht primär der Kontakt der schädlichen tief schmelzenden Phasen mit der Oberfläche des Werkstücks verhindert wird. Sondern es wird bereits die Bildung der schädlichen Substanzen, die zur Hochtemperaturkorrosion führen, dadurch verhindert, dass eine Umwandlung z.B. von tiefschmelzenden Vanadatphasen in hoch schmelzende Vanadate initiiert wird, bzw. die Bildung von tief schmelzenden Vanadaten von vorne herein verhindert wird, indem direkt die Bildung von hoch schmelzenden Vanadaten unter Umgehung der Bildung von tief schmelzenden Vanadaten bevorzugt wird.Essential to the invention is thus that is not prevented by the formation of a surface layer primarily the contact of the harmful deep-melting phases with the surface of the workpiece. But it is already the formation of harmful substances that lead to high-temperature corrosion, thereby preventing that a conversion of, for example, low-melting vanadium phases in high-melting vanadates or the formation of low-melting vanadates is prevented from the outset by directly the formation of high-melting vanadates, bypassing the formation of low-melting vanadates is preferred.
Das heisst, die in den Basiswerkstoff des korrosions-gefährdeten Werkstücks eingebrachten Legierungselemente reagieren mit den Verbrennungsprodukten derart, dass keine tief schmelzenden Phasen entstehen, sondern nur hoch schmelzende Phasen, die bei einer typischen Betriebstemperatur im Brennraum nicht schmelzen und daher nicht die von geschmolzenen Phasen bekannten Korrosionsschäden hervorrufen können.That is, the alloying elements introduced into the base material of the workpiece susceptible to corrosion react with the combustion products such that no deep-melting phases are formed, but only high-melting phases which do not melt at a typical operating temperature in the combustion chamber and therefore do not know those of molten phases Can cause corrosion damage.
Dabei ist es sogar möglich, dass sich die gebildeten hochschmelzenden Vanadatphasen auf der Oberfläche des Bauteils absetzen und so eine zusätzliche Schutzschicht gegen Korrosion und andere chemische oder physikalische Angriffe bilden.In this case, it is even possible that the high-melting vanadium phases formed settle on the surface of the component and thus form an additional protective layer against corrosion and other chemical or physical attacks.
Der Hochtemperaturkorrosionsschutz gemäss der vorliegenden Erfindung hat sich dabei als so effizient herausgestellt, dass der Hochtemperaturkorrosionsschutz gegen tief schmelzende Phasen über weite Temperaturbereiche von einigen wenigen 100°C, zum Beispiel ab 200°C bis zu hohen Temperaturen von 900°C, über 1200°C und sogar bis über 1400°C, unter den verschiedensten Betriebsbedingungen und in ganz unterschiedlichen chemischen Umgebungen, gewährleistet ist. Somit eignet sich der erfindungsgemässe Hochtemperaturkorrosionsschutz nicht nur zum Schutz von Werkstücken, wie den Teilen eines Grossdieselmotors, sondern kann vorteilhaft auf allen Gebieten der Technik wirksam eingesetzt werden, in denen Werkstücke, wie Bauteile oder Maschinenkomponenten von Hochtemperaturkorrosion aufgrund tief schmelzender Phasen, auch unter aggressiven chemischen Randbedingungen und schwierigen Temperaturverhältnissen, bedroht sind.The high-temperature corrosion protection according to the present invention has proved to be so efficient that the high-temperature corrosion protection against deep-melting phases over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high temperatures of 900 ° C, about 1200 ° C. and even up to over 1400 ° C, under a variety of operating conditions and in very different chemical environments, guaranteed. Thus, the high-temperature corrosion protection according to the invention is not only suitable for protecting workpieces, such as the parts of a large diesel engine, but can be used to advantage in all areas of technology, in which workpieces, such as components or machine components of high-temperature corrosion due to deep-melting phases, even under aggressive chemical Boundary conditions and difficult temperature conditions are threatened.
In einem ersten Ausführungsbeispiel eines erfindungsgemässen Werkstücks ist zumindest in einer Randschicht einer Oberfläche des Werkzeugs eines der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co vorgesehen. Es hat sich nämlich herausgestellt, dass diese Elemente sehr effektiv, das heisst mit hoher Ausbeute und hoher Reaktionsgeschwindigkeit genügend hoch schmelzende Phasen, z.B. Vanadate bilden, wenn sie in einer vorgebbaren Konzentration vorgesehen sind, die unter anderem abhängig vom Basiswerkstoff des Werkstücks sein kann, und / oder von der Verbrennungstemperatur bzw. von der Betriebstemperatur des Werkstücks bestimmt sein kann. Es versteht sich, dass die Konzentration und / oder das Mischungsverhältnis der zuvor genannten Legierungselemente, bzw. welche der genannten Legierungselemente vorteilhaft verwendet oder nicht verwendet werden, auch von anderen Randbedingungen als den zuvor genannten abhängen kann. Z.B. unter anderem von der Art und Qualität des verwendeten Brennstoffs oder Treibstoffs, von der Art und Qualität eines eventuell verwendeten Schmierstoffs oder eines anderen Verbrennungszusatzes und vielen anderen Betriebsparametern mehr, unter denen das Werkstück im Betriebszustand betrieben wird.In a first exemplary embodiment of a workpiece according to the invention, one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co. is provided at least in an edge layer of a surface of the tool. It has been found that these elements are very effective, that is with high yield and high reaction rate, sufficiently high melting phases, e.g. Vanadates form, if they are provided in a predetermined concentration, which may be dependent inter alia on the base material of the workpiece, and / or may be determined by the combustion temperature or the operating temperature of the workpiece. It is understood that the concentration and / or the mixing ratio of the abovementioned alloying elements, or which of the abovementioned alloying elements are advantageously used or not used, may also depend on boundary conditions other than those mentioned above. For example, among other things, the nature and quality of the fuel or fuel used, the type and quality of any lubricant used or other combustion additive and many other operating parameters under which the workpiece is operated in the operating condition.
In einem anderen Ausführungsbeispiel ist auf der Oberfläche eines erfindungsgemässen Werkstücks eine Oberflächenschicht vorgesehen, die insbesondere aufgelötet, aufgeschweisst, mechanisch verbunden, schmelztechnisch aufgebracht, heiss-isostatisch aufgepresst oder aufgespritzt, insbesondere thermisch aufgespritzt ist, wobei die Oberflächenschicht eines der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co umfasst. Das ist insbesondere dann von Vorteil, wenn das Werkstück zum Beispiel einem mechanischen Verschleiss an der Oberfläche ausgesetzt ist und die Oberfläche von Zeit zu Zeit in einem Reparaturverfahren erneuert werden muss. Dann kann bei der Reparatur eine neue Oberflächenschicht aufgebracht werden, so dass die Oberfläche des Werkstücks nicht nur mechanisch, also strukturell wieder hergestellt ist, sondern die neu hergestellte Oberflächenschicht auch wieder in ausreichender Konzentration über die vorgenannten Legierungselemente verfügt, so dass die Bildung von tief schmelzenden Phasen auch nach einer Reparatur der Oberfläche weiter zuverlässig verhindert wird.In another exemplary embodiment, a surface layer is provided on the surface of a workpiece according to the invention, which is in particular soldered, welded, mechanically bonded, applied by melting technology, hot-isostatically pressed or sprayed on, in particular thermally sprayed, the surface layer of one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co. This is particularly advantageous when the workpiece, for example, is exposed to mechanical wear on the surface and the surface must be renewed from time to time in a repair process. Then, during the repair, a new surface layer can be applied so that the surface of the workpiece is not only restored mechanically, ie structurally, but the newly prepared surface layer also again in sufficient concentration on the aforementioned alloying elements, so that the formation of deep-melting phases is further reliably prevented even after repair of the surface.
In einem ganz speziellen Ausführungsbeispiel kann dabei die Oberflächenschicht bis auf Verunreinigungen aus reinem Co oder aus reinem Ni bestehen.In a very specific embodiment, the surface layer may consist of impurities of pure Co or of pure Ni.
Bevorzugt liegt dabei der Anteil jedes der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si zwischen 1 %-Gewichtsprozent und 80%-Gewichtsprozent, bevorzugt zwischen 2%-Gewichtsprozent und 70%-Gewichtsprozent und / oder der Anteil von Co und / oder Ni liegt bevorzugt zwischen 1 %-Gewichtsprozent und 99%-Gewichtsprozent, insbesondere bei Verwendung von Eisenbasiswerkstoffen.In this case, the proportion of each of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si is between 1% by weight and 80% by weight, preferably between 2% by weight and 70% by weight and / or the proportion of Co and / or Ni is preferably between 1% and 99% by weight, in particular when using iron-based materials.
Dass der Anteil jedes der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si bevorzugt zwischen 1 %-Gewichtsprozent und 80%-Gewichtsprozent gewählt wird, ist insbesondere darin begründet, dass ausserhalb dieses Konzentrationsbereichs in bestimmten Fällen bzw. unter bestimmten chemischen, physikalischen und thermischen Randbedingungen die Gefahr der Randschichtversprödung besteht.The fact that the proportion of each of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si is preferably selected between 1% weight percent and 80% weight percent is due, in particular, to the fact that outside this concentration range in In certain cases or under certain chemical, physical and thermal boundary conditions there is a risk of surface embrittlement.
Selbstverständlich kann auch das Werkstück insgesamt aus einer Legierung umfassend eines der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe und Co bestehen. Das ist besonders dann von Vorteil, wenn im laufenden Betrieb z.B. eine Oberfläche des Werkstücks mit der Zeit zwar beschädigt oder mehr oder weniger stark abgetragen wird, eine Reparatur des Werkstücks aufgrund seiner Funktion dennoch nicht vorgesehen werden muss. In einem solchen Fall kann die Bildung der tief schmelzenden Phasen auch dann ohne Einbusse der Effizienz gewährleistet werden, wenn z.B. die Oberfläche des Werkstücks mit der Zeit im Betrieb abgetragen oder beschädigt wird. Als Basislegierungen eignen sich dann insbesondere neben Eisenbasislegierungen auch Nickel-, Nickel-Kobalt und / oder Kobaltbasislegierungen.Of course, the workpiece as a whole may consist of an alloy comprising one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe and Co. This is particularly advantageous if during operation, for example, a surface of the workpiece with time is damaged or more or less removed, a repair of the workpiece due to its function still need not be provided. In such a case, the formation of the deep-melting phases can be ensured without sacrificing the efficiency even if, for example, the surface of the workpiece is worn or damaged in operation over time. In addition to iron-base alloys, nickel, nickel-cobalt and / or cobalt-based alloys are then also suitable as base alloys.
Bevorzugt liegt dabei der Anteil jedes der Elemente Co und Ni zwischen 1 %-Gewichtsprozent und 50%-Gewichtsprozent, im Speziellen zwischen 2%-Gewichtsprozent und 35%-Gewichtsprozent, wodurch in bestimmten Fällen verhindert werden kann, dass sich verschiedene mechanische Eigenschaften des Materials, wie z.B. seine Härte, Zähigkeit, Streckgrenze, thermischer Ausdehnungskoeffizient usw. verschlechtern. Insbesondere kann dadurch einer Versprödung des Materials entgegengewirkt werden.Preferably, the proportion of each of the elements Co and Ni is between 1% and 50% by weight, in particular between 2% and 35% by weight, which may in certain cases prevent various mechanical properties of the material , such as its hardness, toughness, yield strength, thermal expansion coefficient, etc. deteriorate. In particular, this can be counteracted by embrittlement of the material.
Wie bereits erläutert ist das Werkstück im Speziellen, aber nicht notwendig, eine Komponente eines Verbrennungssystems einer Brennkraftmaschine, insbesondere eines Zweitakt-Grossdieselmotors, bevorzugt ein Kolben, ein Kolbenring, ein Gaswechselventil, eine Einspritzdüse, eine in einen Brennraum ein- oder angebrachte Komponente, eine einen Brennraum bildende Komponente, wie ein Zylinder und / oder ein Zylinderdeckel, oder eine Komponente eines Turboladers, insbesondere eine Turbine eines Turboladers oder eine Abgas Zu- oder Abführung.As already explained, the workpiece is in particular, but not necessarily, a component of a combustion system of an internal combustion engine, in particular a two-stroke large diesel engine, preferably a piston, a piston ring, a gas exchange valve, an injection nozzle, a component inserted or mounted in a combustion chamber a combustion chamber forming component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or an exhaust gas inlet or outlet.
In einem anderen Fall kann das Werkstück eine Komponente einer Turbine, insbesondere ein Brennraum oder eine Turbinenschaufel einer Gasturbine sein, oder eine Komponente einer Verbrennungsanlage, im Speziellen einer Müllverbrennungsanlage, insbesondere eine Komponente eines Brennraums oder eines Abgassystems einer Verbrennungsanlage sein.In another case, the workpiece may be a component of a turbine, in particular a combustion chamber or a turbine blade of a gas turbine, or a component of an incinerator, in particular a waste incineration plant, in particular a component of a combustion chamber or an exhaust system of a combustion plant.
Weiter betrifft die Erfindung eine Hubkolbenbrennkraftmaschine, insbesondere einen Zweitakt-Grossdieselmotor, eine Turbine oder eine Verbrennungsanlage, insbesondere eine Müllverbrennungsanlage mit einem Werkstück der oben beschriebenen Art mit einem Schutz gegen Hochtemperaturkorrosion durch tief schmelzende Phasen.Furthermore, the invention relates to a reciprocating internal combustion engine, in particular a two-stroke large diesel engine, a turbine or an incinerator, in particular a waste incineration plant with a workpiece of the type described above with a protection against high-temperature corrosion by deep-melting phases.
Die Erfindung betrifft weiter die Verwendung von mindestens einem der Elemente bestehend aus der Gruppe der Elemente Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co zum Schutz eines Werkstücks gegen Hochtemperaturkorrosion durch tief schmelzende Vanadatphasen, wobei das Werkstück an einer Oberfläche mindestens eine Randschicht aufweist, die eines der Elemente bestehend aus der Gruppe der Element Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co umfasst, so dass im Betriebszustand durch eine chemische Reaktion zwischen einem Element bestehend aus der Gruppe der Elemente Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co und dem anwesenden Vanadium und / oder den anwesenden Vanadiumverbindungen und / oder einer tiefschmelzenden Vanadatphase eine hochschmelzende Vanadatphase gebildet wird, so dass die Bildung einer tiefschmelzenden Vanadatphase verhindert wird.The invention further relates to the use of at least one of the group of elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co for protecting a workpiece against High-temperature corrosion by deep-melting vanadate phases, the workpiece having on one surface at least one boundary layer comprising one of the elements consisting of the group of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co, such that in the operating state by a chemical reaction between an element consisting of the group of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co and the vanadium present and / or the vanadium compounds present and / or a low-melting vanadate phase, a high-melting vanadate phase is formed, so that the formation of a low-melting vanadate phase is prevented.
In einem ersten Ausführungsbeispiel wird auf der Oberfläche des Werkstücks eine Oberflächenschicht verwendet, die insbesondere aufgelötet, aufgeschweisst, mechanisch verbunden, schmelztechnisch aufgebracht, heiss-isostatisch aufgepresst oder aufgespritzt, insbesondere thermisch aufgespritzt wird, wobei in der Oberflächenschicht eines der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni und Co vorgesehen wird.In a first embodiment, a surface layer is used on the surface of the workpiece, in particular soldered, welded, mechanically bonded, applied by melting, hot isostatically pressed or sprayed, in particular thermally sprayed, wherein in the surface layer of one of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni and Co are provided.
In einem speziellen Ausführungsbeispiel wird eine Oberflächenschicht verwendet, die bis auf Verunreinigungen aus reinem Co oder aus reinem Ni besteht.In a specific embodiment, a surface layer is used which, except for impurities, consists of pure Co or of pure Ni.
Dabei wird bevorzugt eine chemische Zusammensetzung verwendet, wobei der Anteil jedes der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si zwischen 1 %-Gewichtsprozent und 80%-Gewichtsprozent, bevorzugt zwischen 2%-Gewichtsprozent und 70%-Gewichtsprozent gewählt wird und / oder der Anteil von Co und / oder Ni bevorzugt zwischen 1 %-Gewichtsprozent und 99%-Gewichtsprozent gewählt wird.In this case, preference is given to using a chemical composition in which the proportion of each of the elements from the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si is between 1% by weight and 80% by weight, preferably between 2%. % By weight and 70% weight percent is selected and / or the proportion of Co and / or Ni is preferably selected between 1% weight percent and 99% weight percent.
In einer weiteren Verwendung wird das Werkstück selbst aus einer Legierung umfassend eines der Elemente aus der Gruppe Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe und Co bereit gestellt.In a further use, the workpiece itself is made of an alloy comprising one of the elements of the group Ca, Mg, Ta, Y, Na, Zn, P, B, Si, Ni, Fe and Co.
Insbesondere um eine Verschlechterung der mechanischen Eigenschaften des Werkstücks zu verhindern, wird eine chemische Zusammensetzung verwendet, wobei der Anteil jedes der Elemente Ca, Mg, Ta, Y, Na, Zn, P, B, Si zwischen 1 %-Gewichtsprozent und 50%-Gewichtsprozent, bevorzugt zwischen 2%-Gewichtsprozent und 35%-Gewichtsprozent gewählt wird, insbesondere wenn eine Co-, Fe-, oder Ni-Basislegierung für das Werkstück verwendet wird.In particular, to prevent deterioration of the mechanical properties of the workpiece, a chemical composition is used wherein the proportion of each of the elements Ca, Mg, Ta, Y, Na, Zn, P, B, Si is between 1% weight percent and 50%. Percent by weight, preferably between 2% and 35% by weight, especially when a Co, Fe, or Ni base alloy is used for the workpiece.
In einer für die Praxis sehr wichtigen Verwendung ist das Werkstück eine Komponente eines Verbrennungssystems einer Brennkraftmaschine, insbesondere eines Zweitakt-Grossdieselmotors ist, bevorzugt ein Kolben, ein Kolbenring, ein Gaswechselventil, eine Einspritzdüse, eine einen Brennraum bildende Komponente, wie ein Zylinder und / oder ein Zylinderdeckel, oder eine Komponente eines Turboladers, insbesondere eine Turbine eines Turboladers oder eine Abgas Zu- oder Abführung.In a very important for practical use, the workpiece is a component of a combustion system of an internal combustion engine, in particular a two-stroke large diesel engine, preferably a piston, a piston ring, a gas exchange valve, an injection nozzle, a combustion chamber forming component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or an exhaust gas inlet or outlet.
In einer weiteren wichtigen Verwendung ist das Werkstück eine Komponente einer Turbine, insbesondere ein Brennraum oder eine Turbinenschaufel einer Gasturbine, oder eine Komponente einer Verbrennungsanlage, im Speziellen einer Müllverbrennungsanlage, insbesondere eine Komponente eines Brennraums oder eines Abgassystems einer Verbrennungsanlage.In a further important use, the workpiece is a component of a turbine, in particular a combustion chamber or a turbine blade of a gas turbine, or a component of an incinerator, in particular a waste incineration plant, in particular a component of a combustion chamber or an exhaust system of an incinerator.
Claims (17)
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EP06405297A EP1752561A1 (en) | 2005-08-10 | 2006-07-11 | Article protected against high temperature corrosion and reciprocating pistion internal combustion engine or turbine or combustion unit containing the article |
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EP06405297A EP1752561A1 (en) | 2005-08-10 | 2006-07-11 | Article protected against high temperature corrosion and reciprocating pistion internal combustion engine or turbine or combustion unit containing the article |
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Cited By (2)
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EP2039412A2 (en) | 2007-09-21 | 2009-03-25 | Wärtsilä Schweiz AG | Exhaust gas particle filter and method for manufacturing an exhaust gas particle filter |
EP2434216A1 (en) * | 2010-09-22 | 2012-03-28 | Siemens Aktiengesellschaft | Method for producing a burner |
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DE102010030499A1 (en) * | 2010-06-24 | 2011-12-29 | Man Diesel & Turbo Se | Cylinder head and thus equipped internal combustion engine |
JP2015502478A (en) * | 2011-11-09 | 2015-01-22 | フェデラル−モーグル コーポレイション | Piston ring with wear-resistant cobalt coating |
CN104562006B (en) * | 2013-10-25 | 2018-08-14 | 通用电气公司 | With the element of anti-corrosion layer protection and the method for manufacturing the element |
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Cited By (3)
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EP2039412A3 (en) * | 2007-09-21 | 2010-12-22 | Wärtsilä Schweiz AG | Exhaust gas particle filter and method for manufacturing an exhaust gas particle filter |
EP2434216A1 (en) * | 2010-09-22 | 2012-03-28 | Siemens Aktiengesellschaft | Method for producing a burner |
Also Published As
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CN1912183A (en) | 2007-02-14 |
JP2007046163A (en) | 2007-02-22 |
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