EP1752560A1 - Article protected against high temperature corrosion and reciprocating piston internal combustion engine or turbine or combustion unit containing the article. - Google Patents
Article protected against high temperature corrosion and reciprocating piston internal combustion engine or turbine or combustion unit containing the article. Download PDFInfo
- Publication number
- EP1752560A1 EP1752560A1 EP06405296A EP06405296A EP1752560A1 EP 1752560 A1 EP1752560 A1 EP 1752560A1 EP 06405296 A EP06405296 A EP 06405296A EP 06405296 A EP06405296 A EP 06405296A EP 1752560 A1 EP1752560 A1 EP 1752560A1
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- Prior art keywords
- workpiece
- temperature corrosion
- alloy
- component
- turbine
- Prior art date
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- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 101
- 230000007797 corrosion Effects 0.000 title claims abstract description 101
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 57
- 239000000956 alloy Substances 0.000 claims abstract description 57
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000004056 waste incineration Methods 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 239000011253 protective coating Substances 0.000 abstract description 2
- 229910003336 CuNi Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 239000010949 copper Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 229910018054 Ni-Cu Inorganic materials 0.000 description 10
- 229910018481 Ni—Cu Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 229910002482 Cu–Ni Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007751 thermal spraying Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 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
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product 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
- 239000004035 construction material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910001235 nimonic Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- 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
-
- 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
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2201/00—Metals
- F05C2201/04—Heavy metals
- F05C2201/0469—Other heavy metals
- F05C2201/0475—Copper or alloys thereof
- F05C2201/0484—Nickel-Copper alloy, e.g. monel
Definitions
- the invention relates to a workpiece with protection against high-temperature corrosion, a reciprocating internal combustion engine, in particular two-stroke large diesel engine, a turbine combustion system with a high temperature corrosion protection, and the use of an alloy for protecting a workpiece 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 be, for example, iron, cobalt or nickel or an alloy of these or other 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.
- a corrosion protection coating based on lead and tin which offers in particular a good corrosion protection in humid and saline environments.
- a complicated Cu-Ni-based alloy is proposed as a high-temperature corrosion protection, which comprises P, B, Si, Cr, Fe and C in certain proportions, and is preferably applied in the form of a spray powder in a thermal spraying process on the surface of a workpiece.
- Another Cu-Ni based alloy comprising, among others, Mn, Fe, Si, S and C is used as corrosion protection in the JP 02 132 763 proposed.
- Ni-based alloys are used in the US 4,019,900 especially described as good protection against oxidation.
- 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.
- incinerators for example the components of a combustion chamber of a waste incinerator, 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 the exhaust systems of turbines.
- incinerators for example the components of a combustion chamber of a waste incinerator, 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 the exhaust systems of turbines.
- the skilled person of course a variety of other workpieces are known, which are threatened as components of various devices of hot gas corrosion.
- molten phases in particular during combustion of Heavy oil contain vanadates, such as sodium vanadylvanadates, which are detectable by X-ray analysis.
- the melting that is, the occurrence of the molten phases 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 invention thus relates to a workpiece with protection against high-temperature corrosion, wherein a surface of the workpiece has a high-temperature corrosion protection, which consists except for impurities of an alloy of Cu and Ni.
- the impurities mentioned above are understood to mean those elements which additionally occur in the alloy of Cu and Ni according to the invention and which do not essentially influence the protection against high-temperature corrosion.
- Corresponding impurities which do not substantially influence the high-temperature corrosion protection can be, for example, 0-3% by weight Fe, in particular also less than 2% weight Fe, in particular less than 1% weight Fe, and / or the impurities can be 0-3%, for example.
- Weight percent Mn is less than 2%, for example %
- Mn in particular less than 1% by weight Mn
- / or the impurities can be, for example, 0-3% by weight Co, in particular also less than 2% by weight Co, in particular less than 1% by weight Co
- / or the impurities may for example be 0-3% by weight of Si, in particular also less than 2% by weight of Si, in particular less than 1% by weight of Si
- / or the impurities may contain, for example, 0-3% by weight Zn, in particular eg also less than 2% by weight of Zn, in particular less than 1% by weight of Zn
- / or the impurities can, for example, 0-3% by weight of Al, in particular also less than 2% by weight of Al, in particular less than 1% by weight of Al be, and or other corrosion-relevant impurities in correspondingly small amounts.
- the high-temperature corrosion protection according to the present invention has proven to be so versatile in relation to the various known high-temperature corrosion mechanisms that the high temperature corrosion protection of an alloy of Cu and Ni over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high Temperatures of 900 ° C, over 1200 ° C and even up to over 1400 ° C, under various operating conditions and throughout different chemical environments, can be used advantageously to prevent or reduce high-temperature corrosion.
- the high-temperature corrosion protection according to the invention is not only suitable for the protection of workpieces, such as the parts of a large diesel engine, but can be advantageously used effectively in all areas of technology in which workpieces, such as components or machine components of high-temperature corrosion, even under aggressive chemical boundary conditions, threatened ,
- the alloy of the hot corrosion protection comprises at most 95% weight percent Ni, in particular between 10% and 80% weight percent Ni, and in particular 70% Ni, the remainder being impurities of copper.
- the high-temperature corrosion protection alloy comprises at most 95% by weight of Cu, in particular between 10% and 80% by weight of Cu, in particular 70% of Cu, the remainder being nickel except for impurities.
- the hot corrosion protection for a workpiece according to the invention can be optimized as required.
- the material removal of the anticorrosive layer or of the component itself under given experimental conditions is an easily accessible variable with which the protective effect of different types of coatings can be compared very well in terms of quantity and quality.
- the experimental apparatus used consists of a horizontal tube furnace, which is equipped with a quartz glass tube of 70 mm diameter for receiving the samples.
- the sample space is in the experiment via a gas supply line, in which a humidifier is interposed, fed with gas, so that a defined gas composition is adjustable as a test atmosphere.
- the experimental gas atmosphere consisted essentially of air (N 2 -21% O 2 ) with a water content of 10% volume percent.
- an artificial ash mixture was defined with the following composition: Na 2 CO 3 two mass fractions, V 2 O 5 eight mass fractions, CaSO 4 1.5 mass fractions.
- the samples were placed inside crucibles and surrounded with ash filling.
- the partially provided with thermally sprayed layers samples had a trough-shaped depression in the center for receiving the artificial ash.
- a quartz glass bowl was used to hold the crucible or the ash-covered samples to prevent contamination of the furnace tube by creeping ash.
- the test temperature was continuously 600 ° C.
- a temperature of 650 ° C was set at the start of the test for 20 min. The heating time to this temperature was about one hour.
- the experimental times were between 160 hours and 1100 hours. After the end of the test, the samples were cooled in the oven. This process took about 8 hours.
- Table 1 below shows the result of material removal under the test conditions described above after a service life of 580 Hours for different elements or compounds and / or alloys.
- Table 1 clearly shows that after a corrosion load of 580 hours under the test conditions described above, the Cu-30Ni layers (except for technically insignificant impurities consisting of 70% copper and 30% nickel) or the Ni-30Cu layers (bis to technically insignificant contamination consisting of 70% nickel and 30% copper) by far the lowest material removal and thus were the most corrosion resistant.
- the aforementioned Ni-Cu alloys have a material removal of only 0.055 mm or 0.06 mm after 580 hours, the material removal is at least twice as high for pure chromium or nickel layers as for Ni-Cr alloy Ni-50Cr under the same experimental conditions big, with the 16CrMo4 4 compound even more than 20 times bigger.
- a composition of 70% wt.% Ni and 30% wt.% Cu proves to be particularly advantageous for the protection of components of a large diesel engine, such as the protection of a piston surface, an injection valve, a gas exchange valve, a cylinder wall or a component of the exhaust system, such as for example, the components of an exhaust gas turbocharger system.
- the table shows only some test results.
- the ratio of copper to nickel may vary depending on the nature or chemical composition and / or the temperature of the corrosive environment.
- the thermal expansion coefficient of a corrosion protection coating according to the present invention can be excellently adapted to the expansion coefficient of the material to be coated.
- the high-temperature corrosion protection of the present invention comprises an alloy which, apart from not technically significant impurities, consists only of copper and nickel.
- the high-temperature corrosion protection on the surface of the workpiece is preferably provided as a surface layer which is in particular soldered, welded, hot-isostatically pressed, sprayed on, in particular thermally sprayed, mechanically bonded, applied by melting technology, or applied in any other suitable manner.
- the workpiece itself, if, for example, the mechanical, thermal or other requirements on the workpiece allow, as such from the alloy of High temperature corrosion protection in a composition as exemplified above exist.
- the workpiece is in particular, but not necessary, 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, or one in the combustion chamber - or introduced 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 an incinerator.
- 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 with a high temperature corrosion protection of an alloy of Cu and Ni, as described in detail above.
- the invention further relates to the use of a known alloy for protecting a workpiece against high-temperature corrosion. That is, it is proposed for a surface of the workpiece, a high-temperature corrosion protection for use, which consists of impurities except Cu and Ni.
- an alloy as high-temperature corrosion protection has proven to be particularly advantageous, which comprises at most 95% weight percent Ni, in particular between 10% and 80% weight percent Ni, in particular 70% weight percent Ni and the remainder except for impurities from Cu and / or wherein the high temperature corrosion protection alloy comprises at most 95% wt Cu, more specifically between 10% and 80% wt Cu, more preferably 70% wt Cu, the remainder being Ni.
- a Cu-Ni alloy is used according to the present invention as a high temperature corrosion protection on the surface of the workpiece in the form of a surface layer, in particular soldered, welded, mechanically bonded, applied by melting, hot isostatically pressed or sprayed , in particular thermally sprayed.
- the workpiece itself can be made of the alloy of high temperature corrosion protection, so that, for example, the application of a corresponding layer of a Cu-Ni alloy according to the present invention is not necessary because the workpiece itself and thus its surface consists of a suitable Ni-Cu alloy.
- a Ni-Cu alloy is used as Hochtemperaturkorriosionsschutz for a workpiece which 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, or an im Combustion chamber introduced or introduced component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or exhaust gas inlet or outlet and / or a Ni-Cu alloy is used as a high temperature corrosion protection for a workpiece used, which 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.
- the high-temperature corrosion protection according to the present invention has proven to be so versatile in relation to the various known high-temperature corrosion mechanisms that the high temperature corrosion protection of an alloy of Cu and Ni over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high Temperatures of 900 ° C, over 1200 ° C and even up to over 1400 ° C, under various operating conditions and throughout different chemical environments, can be used advantageously to prevent or reduce high-temperature corrosion.
- the corresponding alloy can be optimally adjusted to specific chemical and / or physical requirements, such as the chemical environment or operating temperature.
- the coefficient of thermal expansion of a Ni-Cu corrosion protection layer can be optimally adjusted by adjusting the Ni-Cu ratio to the expansion coefficient or, for example, to the lattice constants of the workpiece to be protected.
- a ratio of Ni / Cu / Ni of 70/30 can give very good results in terms of high-temperature corrosion protection, other Cu / Ni ratios can be used to protect against high-temperature corrosion in certain cases become.
- the inventive high-temperature corrosion protection can not only be used to protect workpieces, such as the parts of a large diesel engine, but can be advantageously used in all areas of technology in which workpieces, such as components or machine components of high temperature corrosion, even under aggressive chemical boundary conditions threatened.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Cylinder Crankcases Of Internal Combustion Engines (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Exhaust Silencers (AREA)
Abstract
Description
Die Erfindung betrifft ein Werkstück mit einem Schutz gegen Hochtemperaturkorrosion, eine Hubkolbenbrennkraftmaschine, insbesondere Zweitakt-Grossdieselmotor, eine Turbine eine Verbrennungsanlage mit einem Hochtemperaturkorrosionsschutz, sowie die Verwendung einer Legierung zum Schutz eines Werkstücks gegen Hochtemperaturkorrosion gemäss dem Oberbegriff des unabhängigen Anspruchs der jeweiligen Kategorie.The invention relates to a workpiece with protection against high-temperature corrosion, a reciprocating internal combustion engine, in particular two-stroke large diesel engine, a turbine combustion system with a high temperature corrosion protection, and the use of an alloy for protecting a workpiece 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 MCrAlY-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 be, for example, iron, cobalt or nickel or an alloy of these or other 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.
So wird zum Beispiel in der
Damit verwandte Ni-Basis-Legierungen werden in der
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,Thus, especially workpieces, components and machine components that are in more or less direct contact with combustion processes, threatened by high temperature corrosion. Examples include piston surfaces of pistons in internal combustion engines, cylinder walls,
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.Cylinder cover, injectors, gas exchange valves, but also the components of the exhaust systems of internal combustion engines, such as turbochargers, especially turbine parts and / or the exhaust gas supply or discharge of exhaust and turbocharger systems.
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 Heissgaskorrosion bedroht sind.Further examples are the components of incinerators, for example the components of a combustion chamber of a waste incinerator, 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 the exhaust systems of turbines. In addition, the skilled person of course a variety of other workpieces are known, which are threatened as components of various devices of hot gas 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 im Grossdieselmotor zu beobachtenden Hochtemperaturkorrosion geht von schmelzflüssigen Phasen aus. Solche schmelzflüssigen Phasen können insbesondere bei Verbrennung von Schweröl Vanadate enthalten, wie zum Beispiel Natriumvanadylvanadate, die unter anderem röntgenographisch nachweisbar sind.A significant influence of the high-temperature corrosion observed in the large diesel engine is based on molten phases. Such molten phases, in particular during combustion of Heavy oil contain vanadates, such as sodium vanadylvanadates, which are detectable by X-ray analysis.
Dieses Phänomen wurde zum Beispiel von Schlager in dem Artikel "
Beim Betrieb eines Dieselmotors kann die Aufschmelzung, das heisst das Auftreten der schmelzflüssigen 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.When operating a diesel engine, the melting, that is, the occurrence of the molten phases from about 400 ° C can be observed. Among other things, such 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.
Dabei sind die zuvor exemplarisch beschriebenen Probleme mit den schmelzflüssigen Vanadat Phasen nur ein Beispiel für einen Mechanismus, der zu Hochtemperaturkorrosion führt. Dem Fachmann sind eine Vielzahl weiterer Mechanismen und Heisskorrosionseffekte bekannt, 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.The problems described above by way of example with the molten vanadate phases are only one example of a mechanism which leads to high-temperature corrosion. A variety of other mechanisms and hot corrosion effects are known in the art, which are also observed, not only in diesel engines, and can lead to the known corrosion damage in operation, for example in the above-mentioned systems and / or on the components mentioned in the operation.
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. So 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 Heisskorrosion zwar minimiert, aber letztlich nicht im notwendigen Umfang verhindert wird.Although, 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. Thus, 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 are always optimized with respect to certain corrosion processes, so that ultimately a certain surface protection layer always represents a compromise, so that Although the hot corrosion is minimized, but ultimately not prevented to the extent necessary.
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 Haupt-Materialien bereitgestellt wird, das korrosionsgeschützte Werkstück somit besonders wirtschaftlich und einfach herstellbar ist, wobei das Werkstück gleichzeitig gegen im wesentlichen alle im Betriebszustand auf das Werkstück einwirkenden Heisskorrosionsmechanismen 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 main materials, the corrosion-protected workpiece is thus particularly economical and easy to produce, the workpiece at the same time effectively protected against essentially all hot corrosion mechanisms acting on the workpiece during operation.
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, wobei eine Oberfläche des Werkstücks einen Hochtemperaturkorrosionsschutz aufweist, der bis auf Verunreinigungen aus einer Legierung aus Cu und Ni besteht.The invention thus relates to a workpiece with protection against high-temperature corrosion, wherein a surface of the workpiece has a high-temperature corrosion protection, which consists except for impurities of an alloy of Cu and Ni.
Wobei im Rahmen dieser Anmeldung unter den zuvor erwähnten Verunreinigungen solche eventuell in der erfindungsgemässen Legierung aus Cu und Ni zusätzlich vorkommenden Elemente verstanden werden, die den Schutz gegen Hochtemperaturkorrosion im wesentlichen nicht beeinflussen. Entsprechende, den Hochtemperaturkorrosionsschutz im wesentlichen nicht beeinflussenden Verunreinigungen können zum Beispiel 0 - 3% Gewichtsprozent Fe, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Fe, insbesondere weniger als 1 % Gewichtsprozent Fe sein und / oder die Verunreinigungen können zum Beispiel 0 - 3% Gewichtsprozent Mn, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Mn, insbesondere weniger als 1 % Gewichtsprozent Mn sein, und / oder die Verunreinigungen können zum Beispiel 0 - 3% Gewichtsprozent Co, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Co, insbesondere weniger als 1 % Gewichtsprozent Co sein, und / oder die Verunreinigungen können zum Beispiel 0 - 3% Gewichtsprozent Si, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Si, insbesondere weniger als 1 % Gewichtsprozent Si sein, und / oder die Verunreinigungen können zum Beispiel 0-3% Gewichtsprozent Zn, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Zn, insbesondere weniger als 1 % Gewichtsprozent Zn sein, und / oder die Verunreinigungen können zum Beispiel 0 - 3% Gewichtsprozent AI, im Speziellen z.B. auch weniger als 2 % Gewichtsprozent Al, insbesondere weniger als 1 % Gewichtsprozent AI sein, und oder sonstige korrosionstechnisch nicht relevante Verunreinigungen in entsprechend geringen Mengen sein.For the purposes of this application, the impurities mentioned above are understood to mean those elements which additionally occur in the alloy of Cu and Ni according to the invention and which do not essentially influence the protection against high-temperature corrosion. Corresponding impurities which do not substantially influence the high-temperature corrosion protection can be, for example, 0-3% by weight Fe, in particular also less than 2% weight Fe, in particular less than 1% weight Fe, and / or the impurities can be 0-3%, for example. Weight percent Mn, especially less than 2%, for example % By weight Mn, in particular less than 1% by weight Mn, and / or the impurities can be, for example, 0-3% by weight Co, in particular also less than 2% by weight Co, in particular less than 1% by weight Co, and / or the impurities may for example be 0-3% by weight of Si, in particular also less than 2% by weight of Si, in particular less than 1% by weight of Si, and / or the impurities may contain, for example, 0-3% by weight Zn, in particular eg also less than 2% by weight of Zn, in particular less than 1% by weight of Zn, and / or the impurities can, for example, 0-3% by weight of Al, in particular also less than 2% by weight of Al, in particular less than 1% by weight of Al be, and or other corrosion-relevant impurities in correspondingly small amounts.
Es hat sich nämlich völlig überraschend gezeigt, dass eine einfache Legierung aus Kupfer und Nickel gegen relevante Hochtemperaturkorrosionsmechanismen, insbesondere, aber nicht nur, gegen beim Betrieb eines Grossdieselmotors auftretenden relevanten Hochtemperaturkorrosionsmechanismen in hervorragender Weise gleichzeitig Schutz bietet. Insbesondere die schädlichen Wirkungen der bei der Schwerölverbrennung auftretenden schmelzflüssigen Vanadat Phasen werden durch den erfindungsgemässen Hochtemperaturkorrosionsschutz aus einer Legierung aus Cu und Ni wirksam vermieden oder reduziert.It has surprisingly been found that a simple alloy of copper and nickel against relevant high-temperature corrosion mechanisms, in particular, but not only, against the occurring during operation of a large diesel engine relevant high temperature corrosion mechanisms in an excellent way simultaneously provides protection. In particular, the harmful effects of molten vanadate phases occurring during heavy oil combustion are effectively avoided or reduced by the inventive high-temperature corrosion protection of an alloy of Cu and Ni.
Der Hochtemperaturkorrosionsschutz gemäss der vorliegenden Erfindung hat sich dabei als so vielseitig in Bezug auf die verschiedenen bekannten Hochtemperaturkorrosionsmechanismen herausgestellt, dass der Hochtemperaturkorrosionsschutz aus einer Legierung aus Cu und Ni 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, vorteilhaft zur Verhinderung oder Reduzierung von Hochtemperaturkorrosion einsetzbar 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, auch unter aggressiven chemischen Randbedingungen, bedroht sind.The high-temperature corrosion protection according to the present invention has proven to be so versatile in relation to the various known high-temperature corrosion mechanisms that the high temperature corrosion protection of an alloy of Cu and Ni over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high Temperatures of 900 ° C, over 1200 ° C and even up to over 1400 ° C, under various operating conditions and throughout different chemical environments, can be used advantageously to prevent or reduce high-temperature corrosion. Thus, the high-temperature corrosion protection according to the invention is not only suitable for the protection of workpieces, such as the parts of a large diesel engine, but can be advantageously used effectively in all areas of technology in which workpieces, such as components or machine components of high-temperature corrosion, even under aggressive chemical boundary conditions, threatened ,
In einem ersten Ausführungsbeispiel eines erfindungsgemässen Werkstücks umfasst die Legierung des Heisskorrosionsschutzes höchstens 95%-Gewichtsprozent Ni, im speziellen zwischen 10% und 80% Gewichtsprozent Ni, und im besonderen 70% Ni, wobei der Rest bis auf Verunreinigungen aus Kupfer besteht.In a first exemplary embodiment of a workpiece according to the invention, the alloy of the hot corrosion protection comprises at most 95% weight percent Ni, in particular between 10% and 80% weight percent Ni, and in particular 70% Ni, the remainder being impurities of copper.
Dabei umfasst die Legierung des Hochtemperaturkorrosionsschutzes in einem anderen Fall höchstens 95%-Gewichtsprozent Cu, im speziellen zwischen 10% und 80% Gewichtsprozent Cu, im besonderen 70% Cu, wobei der Rest bis auf Verunreinigungen aus Nickel besteht.In another case, the high-temperature corrosion protection alloy comprises at most 95% by weight of Cu, in particular between 10% and 80% by weight of Cu, in particular 70% of Cu, the remainder being nickel except for impurities.
Durch die spezielle Wahl des Anteils an Cu und / oder Ni kann der Heisskorrosionsschutz für ein erfindungsgemässes Werkstück je nach Anforderung optimiert werden.Due to the special choice of the proportion of Cu and / or Ni, the hot corrosion protection for a workpiece according to the invention can be optimized as required.
Dabei ist zur Charakterisierung der Korrosionsfestigkeit der Materialabtrag der Korrosionsschutzschicht bzw. des Bauteils selbst unter vorgegebenen experimentellen Bedingungen eine leicht zugängliche Grösse, mit der sich die Schutzwirkung verschiedenartiger Beschichtungen quantitativ und qualitativ sehr gut vergleichen lassen.In order to characterize the corrosion resistance, the material removal of the anticorrosive layer or of the component itself under given experimental conditions is an easily accessible variable with which the protective effect of different types of coatings can be compared very well in terms of quantity and quality.
Zur Charakterisierung von Werkstücken mit einem erfindungsgemässen Schutz gegen Hochtemperaturkorrosion zum Vergleich mit bekannten Legierungen, wurde das Korrosionsverhalten verschiedener Elemente und Legierungen systematisch untersucht.For the characterization of workpieces with an inventive protection against high-temperature corrosion for comparison with known Alloys, the corrosion behavior of various elements and alloys was systematically investigated.
Die verwendete Versuchsapparatur besteht aus einem Horizontalrohrofen, der mit einem Quarzglasrohr von 70 mm Durchmesser zur Aufnahme der Proben ausgerüstet ist. Der Probenraum wird im Experiment über eine Gaszuleitung, in welche eine Befeuchtungseinrichtung zwischengeschaltet ist, mit Gas beschickt, so dass eine definierte Gaszusammensetzung als Versuchsatmosphäre einstellbar ist.The experimental apparatus used consists of a horizontal tube furnace, which is equipped with a quartz glass tube of 70 mm diameter for receiving the samples. The sample space is in the experiment via a gas supply line, in which a humidifier is interposed, fed with gas, so that a defined gas composition is adjustable as a test atmosphere.
Die Versuchsgasatmosphäre bestand im wesentlichen aus Luft (N2-21 % O2) mit einem Wassergehalt von 10%-Volumenprozent. Um die bei der Verbrennung von Schweröl, das als Treibstoff bei Großdieselmotoren eingesetzt wird, entstehenden Beiträge zu simulieren, wurde eine künstliche Aschemischung mit folgender Zusammensetzung definiert: Na2CO3 zwei Massenanteile, V2O5 acht Massenanteile, CaSO4 1.5 Masseanteile.The experimental gas atmosphere consisted essentially of air (N 2 -21% O 2 ) with a water content of 10% volume percent. In order to simulate the contributions to the combustion of heavy fuel oil used as fuel in large diesel engines, an artificial ash mixture was defined with the following composition: Na 2 CO 3 two mass fractions, V 2 O 5 eight mass fractions, CaSO 4 1.5 mass fractions.
Die Proben wurden innerhalb von Tiegeln platziert und mit einer Aschefüllung umgeben. Die teils mit mit thermisch gespritzten Schichten versehenen Proben besaßen mittig eine muldenförmige Vertiefung zur Aufnahme der künstlichen Asche. Eine Quarzglasschale diente zur Aufnahme der Tiegel bzw. der mit Asche bedeckten Proben, um eine Kontamination des Ofenrohres durch kriechende Asche zu vermeiden. Die Versuchstemperatur betrug durchgehend 600°C. Um ein Aufschmelzen der künstlichen Asche sicherzustellen, wurde bei Versuchsbeginn für 20 Min. eine Temperatur von 650°C eingestellt. Die Aufheizdauer auf diese Temperatur betrug etwa eine Stunde. Die Versuchszeiten betrugen zwischen 160 Stunden und 1100 Stunden. Nach Beendigung der Versuchsdauer wurden die Proben im Ofen abgekühlt. Dieser Vorgang benötigte etwa 8 Stunden.The samples were placed inside crucibles and surrounded with ash filling. The partially provided with thermally sprayed layers samples had a trough-shaped depression in the center for receiving the artificial ash. A quartz glass bowl was used to hold the crucible or the ash-covered samples to prevent contamination of the furnace tube by creeping ash. The test temperature was continuously 600 ° C. To ensure melting of the artificial ash, a temperature of 650 ° C was set at the start of the test for 20 min. The heating time to this temperature was about one hour. The experimental times were between 160 hours and 1100 hours. After the end of the test, the samples were cooled in the oven. This process took about 8 hours.
Die nachfolgende Tabelle 1 zeigt das Ergebnis des Materialabtrags unter den zuvor beschriebenen Versuchsbedingungen nach einer Standzeit von 580 Stunden für verschiedene Elemente bzw. Verbindungen und / oder Legierungen.Table 1 below shows the result of material removal under the test conditions described above after a service life of 580 Hours for different elements or compounds and / or alloys.
Tabelle 1 zeigt deutlich, dass nach einer Korrosionsbelastung von 580 Stunden unter den oben beschriebenen Versuchsbedingungen, die Cu-30Ni-Schichten (bis auf technisch unbedeutende Verunreinigungen bestehend aus 70% Kupfer und 30% Nickel) bzw. die Ni-30Cu-Schichten (bis auf technisch unbedeutende Verunreinigungen bestehend aus 70% Nickel und 30% Kupfer) den bei weitem geringsten Materialabtrag aufweisen und damit am korrosionsbeständigsten waren.Table 1 clearly shows that after a corrosion load of 580 hours under the test conditions described above, the Cu-30Ni layers (except for technically insignificant impurities consisting of 70% copper and 30% nickel) or the Ni-30Cu layers (bis to technically insignificant contamination consisting of 70% nickel and 30% copper) by far the lowest material removal and thus were the most corrosion resistant.
Währen die zuvor genannten Ni-Cu-Legierungen nach 580 Stunden einen Materialabtrag von nur 0.055 mm bzw. 0.06 mm aufweisen, ist der Materialabtrag bei reinen Chrom oder Nickel Schichten, bei der Ni-Cr-Legierung Ni-50Cr unter gleichen Versuchsbedingungen mindestens doppelt so gross, bei der 16CrMo4 4 Verbindung sogar mehr als 20 mal grösser.Whereas the aforementioned Ni-Cu alloys have a material removal of only 0.055 mm or 0.06 mm after 580 hours, the material removal is at least twice as high for pure chromium or nickel layers as for Ni-Cr alloy Ni-50Cr under the same experimental conditions big, with the 16CrMo4 4 compound even more than 20 times bigger.
Es wird somit deutlich, dass zwar bei allen in der Tabelle angegebenen Werkstoffen eine erhebliche Verbesserung der Korrosionsbeständigkeit gegenüber dem Konstruktionswerkstoff für Großdieselmotorenkolben 16CrMo44 erreicht werden konnte.
Völlig überraschend ist jedoch die hervorragende Beständigkeit der Ni-Cu-Legierungen, die bis auf Verunreinigungen keine weiteren Legierungselemente enthalten, vor allem vor dem Hintergrund des bekannten katastrophalen Versagens von reinem Kupfer unter Korrosionsbedingungen. Eine abschliessende Erklärung für dieses Verhalten kann derzeit noch nicht gegeben werden.However, the outstanding resistance of the Ni-Cu alloys, which contain no other alloying elements apart from impurities, is completely surprising, above all against the background of the known catastrophic failure of pure copper under corrosion conditions. A conclusive explanation for this behavior can not yet be given.
Somit erweist sich insbesondere eine Zusammensetzung aus 70%-Gewichtsprozent Ni und 30%-Gewichtsprozent Cu als besonders vorteilhaft für den Schutz von Komponenten eines Grossdieselmotors, wie den Schutz einer Kolbenoberfläche, eines Einspritzventils, eines Gaswechselventils, einer Zylinderwand oder einer Komponente des Abgassystems, wie zum Beispiel den Komponenten eines Abgas-Turbolader-Systems.Thus, in particular, a composition of 70% wt.% Ni and 30% wt.% Cu proves to be particularly advantageous for the protection of components of a large diesel engine, such as the protection of a piston surface, an injection valve, a gas exchange valve, a cylinder wall or a component of the exhaust system, such as for example, the components of an exhaust gas turbocharger system.
Vergleichbar gute Ergebnisse in Bezug auf den Schutz gegen Hochtemperaturkorrosion erzielt man offenbar auch, wenn die Legierung des Hochtemperaturkorrosionsschutzes aus 70%-Gewichtsprozent Cu und 30%-Gewichtsprozent Ni besteht, was zeigt, dass eine reine Ni-Cu-Legierungen in einem breiten Konzentrationsverhältnis von Ni/Cu einen hervorragenden Hochtemperaturkorrosionsschutz bieten.Comparably good results in terms of protection against high-temperature corrosion apparently also obtained when the alloy of high temperature corrosion protection consists of 70% wt Cu and 30% wt Ni, which shows that a pure Ni-Cu alloys in a broad concentration ratio of Ni / Cu provide excellent high temperature corrosion protection.
Dabei zeigt die Tabelle exemplarisch nur einige Versuchsergebnisse. Wie erwähnt versteht es sich, dass je nach speziellen Anforderungen auch eine andere Zusammensetzung von Cu und Ni zu sehr guten Ergebnissen in Bezug auf den Korrosionsschutz führen. So kann z.B. das Verhältnis von Kupfer zu Nickel je nach Art bzw. chemischer Zusammensetzung und / oder der Temperatur der korrodierenden Umgebung variieren. Oder je nach Material, Form oder Art des Bauteils kann es z.B. möglich sein das Cu-Ni-Verhältnis in Bezug auf andere Parameter, z.B. auf physikalische Eigenschaften des Bauteils abzustimmen. So kann es z.B. von Vorteil sein, das Ni-Cu-Verhältnis auf einen Wert einzustellen, der gleichzeitig einen optimalen Korrisionsschutz gewährleistet und andererseits zu einem Wert des thermischen Ausdehnungskoeffizienten der Korrosionsschutzschicht führt, der optimal an den thermischen Ausdehnungskoeffizienten des zu schützenden Bauteils angepasst ist. Wie die Tabelle deutlich zeigt, lässt sich nämlich insbesondere der thermische Ausdehnungskoeffizient einer Korrosionsschutzbeschichtung gemäss der vorliegenden Erfindung hervorragend auf den Ausdehnungskoeffizienten des zu beschichtenden Materials anpassen.The table shows only some test results. As mentioned, it is understood that, depending on the specific requirements, also a different composition of Cu and Ni lead to very good results in terms of corrosion protection. For example, the ratio of copper to nickel may vary depending on the nature or chemical composition and / or the temperature of the corrosive environment. Or, depending on the material, shape or type of the component, it may be possible, for example, to adjust the Cu / Ni ratio with regard to other parameters, for example physical properties of the component. For example, it may be advantageous to set the Ni-Cu ratio to a value which simultaneously ensures optimum corrosion protection and, on the other hand, to a value of coefficient of thermal expansion of the corrosion protection layer leads, which is optimally adapted to the thermal expansion coefficient of the component to be protected. As the table clearly shows, namely, in particular, the thermal expansion coefficient of a corrosion protection coating according to the present invention can be excellently adapted to the expansion coefficient of the material to be coated.
Ähnliche Anpassungen können selbstverständlich vorteilhaft auch in Bezug auf andere chemische und / oder physikalische Randbedingungen vorgenommen werden, wie z.B. eine Anpassung der Gitterkonstanten der Schicht aus einer Ni-Cu-Legierung auf die Gitterkonstanten des Materials, aus dem das beschichtete Werkstück besteht, um neben dem Hochtemperaturkorrosionsschutz noch weitere gewünschte Wirkungen zu erzielen.Of course, similar adjustments may also be made advantageously with respect to other chemical and / or physical constraints, such as e.g. an adaptation of the lattice constants of the layer of a Ni-Cu alloy to the lattice constants of the material of which the coated workpiece consists, in order to achieve other desired effects in addition to the high-temperature corrosion protection.
Somit ist klar, dass auch ein anderes Verhältnis von Kupfer zu Nickel als das in der Tabelle 1 angegebene vorteilhaft sein kann. Massgebend ist nur, dass der Hochtemperaturkorrosionsschutz der vorliegenden Erfindung eine Legierung umfasst, die, abgesehen von technisch nicht bedeutenden Verunreinigungen, nur aus Kupfer und Nickel besteht.Thus, it is clear that also a different ratio of copper to nickel than that shown in Table 1 can be advantageous. All that matters is that the high-temperature corrosion protection of the present invention comprises an alloy which, apart from not technically significant impurities, consists only of copper and nickel.
Bevorzugt ist dabei der Hochtemperaturkorrosionsschutz auf der Oberfläche des Werkstücks als eine Oberflächenschicht vorgesehen, die insbesondere aufgelötet, aufgeschweisst, heiss-isostatisch aufgepresst, aufgespritzt, insbesondere thermisch gespritzt, mechanisch verbunden, schmelztechnisch aufgebracht, oder in jeder anderen geeigneten Art aufgebracht ist.The high-temperature corrosion protection on the surface of the workpiece is preferably provided as a surface layer which is in particular soldered, welded, hot-isostatically pressed, sprayed on, in particular thermally sprayed, mechanically bonded, applied by melting technology, or applied in any other suitable manner.
Je nach Anwendung kann das Werkstück selbst, wenn z.B. die mechanischen, thermischen oder anderen Anforderungen an das Werkstück dies zulassen, als solches aus der Legierung des Hochtemperaturkorrosionsschutzes in einer Zusammensetzung wie oben exemplarisch angegeben, bestehen.Depending on the application, the workpiece itself, if, for example, the mechanical, thermal or other requirements on the workpiece allow, as such from the alloy of High temperature corrosion protection in a composition as exemplified above exist.
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 einen Brennraum bildende Komponente, oder eine im Brennraum an- oder eingebrachte 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 necessary, 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, or one in the combustion chamber - or introduced 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.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 an incinerator.
Weiter betrifft die Erfindung eine Hubkolbenbrennkraftmaschine, insbesondere einen Zweitakt-Grossdieselmotor, eine Turbine oder eine Verbrennungsanlage, insbesondere eine Müllverbrennungsanlage mit einem Werkstück mit einem Hochtemperaturkorrosionsschutz aus einer Legierung aus Cu und Ni, wie er oben ausführlich beschrieben ist.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 with a high temperature corrosion protection of an alloy of Cu and Ni, as described in detail above.
Die Erfindung betrifft weiterhin die Verwendung einer an sich bekannten Legierung zum Schutz eines Werkstücks gegen Hochtemperaturkorrosion. Das heisst, es wird für eine Oberfläche des Werkstücks ein Hochtemperaturkorrosionsschutz zur Verwendung vorgeschlagen, der bis auf Verunreinigungen nur aus Cu und Ni besteht.The invention further relates to the use of a known alloy for protecting a workpiece against high-temperature corrosion. That is, it is proposed for a surface of the workpiece, a high-temperature corrosion protection for use, which consists of impurities except Cu and Ni.
Wie oben bereits erwähnt, hat sich in überraschenderweise ergeben, dass eine an sich bekannte Legierung, die bis auf Verunreinigungen nur aus Nickel und Kupfer besteht, sich hervorragend als Schutz gegen Hochtemperaturkorrosion eignet, insbesondere, aber nicht nur, in Gegenwart von korrosiv wirkenden Vanadatphasen.As already mentioned above, it has surprisingly been found that an alloy which is known per se and which, except for impurities, consists only of nickel and copper, is outstandingly suitable as protection against High-temperature corrosion is suitable, in particular, but not only, in the presence of corrosive Vanadatphasen.
Dabei hat sich die Verwendung einer Legierung als Hochtemperaturkorrosionsschutz als besonders vorteilhaft gezeigt, die höchstens 95%-Gewichtsprozent Ni, im speziellen zwischen 10% und 80% Gewichtsprozent Ni, im besonderen 70%-Gewichtsprozent Ni umfasst und wobei der Rest bis auf Verunreinigungen aus Cu besteht, und / oder wobei die Legierung des Hochtemperaturkorrosionsschutzes höchstens 95%-Gewichtsprozent Cu, im speziellen zwischen 10% und 80%-Gewichtsprozent Cu, im besonderen 70%-Gewichtsprozent Cu umfasst und der Rest bis auf Verunreinigungen aus Ni besteht.The use of an alloy as high-temperature corrosion protection has proven to be particularly advantageous, which comprises at most 95% weight percent Ni, in particular between 10% and 80% weight percent Ni, in particular 70% weight percent Ni and the remainder except for impurities from Cu and / or wherein the high temperature corrosion protection alloy comprises at most 95% wt Cu, more specifically between 10% and 80% wt Cu, more preferably 70% wt Cu, the remainder being Ni.
In einer für die Praxis besonders wichtigen Anwendung, wird eine Cu-Ni Legierung gemäss der vorliegenden Erfindung als Hochtemperaturkorrosionsschutz auf der Oberfläche des Werkstücks in Form einer Oberflächenschicht verwendet, die insbesondere aufgelötet, aufgeschweisst, mechanisch verbunden, schmelztechnisch aufgebracht, heiss-isostatisch aufgepresst oder aufgespritzt, insbesondere thermisch aufgespritzt wird.In a particularly important application in practice, a Cu-Ni alloy is used according to the present invention as a high temperature corrosion protection on the surface of the workpiece in the form of a surface layer, in particular soldered, welded, mechanically bonded, applied by melting, hot isostatically pressed or sprayed , in particular thermally sprayed.
In einer weiteren Verwendung kann auch das Werkstück selbst aus der Legierung des Hochtemperaturkorrosionsschutzes gefertigt werden, so dass zum Beispiel das Aufbringen einer entsprechenden Schicht aus einer Cu-Ni-Legierung gemäss der vorliegenden Erfindung gar nicht notwendig ist, weil das Werkstück selbst und damit seine Oberfläche aus einer geeigneten Ni-Cu-Legierung besteht.In a further use, the workpiece itself can be made of the alloy of high temperature corrosion protection, so that, for example, the application of a corresponding layer of a Cu-Ni alloy according to the present invention is not necessary because the workpiece itself and thus its surface consists of a suitable Ni-Cu alloy.
Bevorzugt wird eine Ni-Cu-Legierung als Hochtemperaturkorriosionsschutz für ein Werkstück verwendet, das 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, oder eine im Brennraum an- oder eingebrachte Komponente, wie ein Zylinder und / oder ein Zylinderdeckel, oder eine Komponente eines Turboladers, insbesondere eine Turbine eines Turboladers oder eine Abgas Zu- oder Abführung ist und / oder eine Ni-Cu-Legierung wird als Hochtemperaturkorrosionsschutz für ein Werkstück verwendet, das eine Komponente einer Turbine ist, 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 ist.Preferably, a Ni-Cu alloy is used as Hochtemperaturkorriosionsschutz for a workpiece which 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, or an im Combustion chamber introduced or introduced component, such as a cylinder and / or a cylinder cover, or a component of a turbocharger, in particular a turbine of a turbocharger or exhaust gas inlet or outlet and / or a Ni-Cu alloy is used as a high temperature corrosion protection for a workpiece used, which 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.
Es hat sich somit völlig überraschend gezeigt, dass eine einfache Legierung aus Kupfer und Nickel, die bis auf technisch irrelevante Verunreinigungen keine weiteren Legierungselemente umfasst, gegen Hochtemperaturkorrosionsmechanismen, insbesondere, aber nicht nur, gegen verschiedene, beim Betrieb eines Grossdieselmotors auftretenden relevanten Hochtemperaturkorrosionsmechanismen in hervorragender Weise gleichzeitig Schutz bietet. Insbesondere die schädlichen Wirkungen der bei der Schwerölverbrennung auftretenden schmelzflüssigen Vanadat Phasen werden durch den erfindungsgemässen Hochtemperaturkorrosionsschutz aus einer Legierung aus Cu und Ni wirksam vermieden oder zumindest massiv reduziert.It has thus been found, completely surprisingly, that a simple alloy of copper and nickel, which does not comprise any other alloying elements except technically irrelevant impurities, against high-temperature corrosion mechanisms, in particular, but not only, against various relevant high-temperature corrosion mechanisms occurring during operation of a large diesel engine in an excellent manner provides protection at the same time. In particular, the harmful effects of the molten vanadate phases occurring during heavy oil combustion are effectively avoided or at least massively reduced by the high-temperature corrosion protection of an alloy of Cu and Ni according to the invention.
Der Hochtemperaturkorrosionsschutz gemäss der vorliegenden Erfindung hat sich dabei als so vielseitig in Bezug auf die verschiedenen bekannten Hochtemperaturkorrosionsmechanismen herausgestellt, dass der Hochtemperaturkorrosionsschutz aus einer Legierung aus Cu und Ni 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, vorteilhaft zur Verhinderung oder Reduzierung von Hochtemperaturkorrosion einsetzbar ist.The high-temperature corrosion protection according to the present invention has proven to be so versatile in relation to the various known high-temperature corrosion mechanisms that the high temperature corrosion protection of an alloy of Cu and Ni over wide temperature ranges of a few 100 ° C, for example from 200 ° C to high Temperatures of 900 ° C, over 1200 ° C and even up to over 1400 ° C, under various operating conditions and throughout different chemical environments, can be used advantageously to prevent or reduce high-temperature corrosion.
Darüber hinaus kann durch die Einstellung des Verhältnisses von Nickel zu Kupfer die entsprechende Legierung optimal auf spezielle chemische und / oder physikalische Erfordernisse, wie zum Beispiel die chemische Umgebung oder die Temperatur im Betriebszustand eingestellt werden. So kann z.B. der thermische Ausdehnungskoeffizient einer Ni-Cu-Korrosionsschutzschicht durch Einstellung des Ni-Cu-Verhältnisses optimal auf den Ausdehnungskoeffizienten oder zum Beispiel auf die Gitterkonstanten des zu schützenden Werkstücks eingestellt werden.In addition, by adjusting the ratio of nickel to copper, the corresponding alloy can be optimally adjusted to specific chemical and / or physical requirements, such as the chemical environment or operating temperature. Thus, e.g. the coefficient of thermal expansion of a Ni-Cu corrosion protection layer can be optimally adjusted by adjusting the Ni-Cu ratio to the expansion coefficient or, for example, to the lattice constants of the workpiece to be protected.
Auch wenn in bestimmten Fällen z.B., wie oben gezeigt ein Verhältnis von Ni/bzw Cu/Ni von 70/30 zu sehr guten Ergebnissen in Bezug auf Hochtemperaturkorrosionsschutz führen kann, können in bestimmten Fällen auch andere Cu/Ni Verhältnisse vorteilhaft zum Schutz vor Hochtemperaturkorrosion eingesetzt werden.Although in certain cases, as shown above, a ratio of Ni / Cu / Ni of 70/30 can give very good results in terms of high-temperature corrosion protection, other Cu / Ni ratios can be used to protect against high-temperature corrosion in certain cases become.
Der erfindungsgemässe Hochtemperaturkorrosionsschutz kann 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, auch unter aggressiven chemischen Randbedingungen, bedroht sind.The inventive high-temperature corrosion protection can not only be used to protect workpieces, such as the parts of a large diesel engine, but can be advantageously used in all areas of technology in which workpieces, such as components or machine components of high temperature corrosion, even under aggressive chemical boundary conditions threatened.
Claims (15)
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EP06405296A EP1752560B1 (en) | 2005-08-10 | 2006-07-11 | Large diesel engine protected against high temperature corrosion and use of an alloy in a large diesel engine for protecting against high temperature corrosion. |
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Cited By (3)
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EP2182094A1 (en) * | 2008-10-31 | 2010-05-05 | Wärtsilä Schweiz AG | Cylinder for a large diesel motor |
CN102428258A (en) * | 2009-05-20 | 2012-04-25 | 株式会社Ihi | Method for producing impeller applied to supercharger |
DE102020107749A1 (en) | 2020-03-20 | 2021-09-23 | Peter Amborn | Method for avoiding oxidation of the surface of a metallic substrate and metallic substrate produced according to the method |
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CN105710321B (en) * | 2016-04-20 | 2018-01-05 | 包头市科锐微磁新材料有限责任公司 | A kind of neodymium iron boron fast melt-quenching stove nozzle flow-guiding bar |
US20180195613A1 (en) * | 2017-01-06 | 2018-07-12 | Materion Corporation | Piston compression rings of copper-beryllium alloys |
CN111705237B (en) * | 2020-06-03 | 2021-12-14 | 河海大学 | Corrosion-resistant, anti-fouling and anti-cavitation copper-based intermediate entropy alloy coating for ship propeller and preparation method thereof |
CN114318207B (en) * | 2021-12-31 | 2022-11-04 | 西安交通大学 | Preparation method of metal alloy thermal barrier coating sprayed by atmosphere plasma and corresponding copper alloy base material |
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- 2006-07-11 AT AT06405296T patent/ATE472618T1/en active
- 2006-07-11 DK DK06405296.2T patent/DK1752560T3/en active
- 2006-07-11 EP EP06405296A patent/EP1752560B1/en not_active Not-in-force
- 2006-07-31 KR KR1020060072223A patent/KR101365928B1/en not_active IP Right Cessation
- 2006-08-09 JP JP2006216420A patent/JP5052838B2/en not_active Expired - Fee Related
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CN102428258A (en) * | 2009-05-20 | 2012-04-25 | 株式会社Ihi | Method for producing impeller applied to supercharger |
DE102020107749A1 (en) | 2020-03-20 | 2021-09-23 | Peter Amborn | Method for avoiding oxidation of the surface of a metallic substrate and metallic substrate produced according to the method |
Also Published As
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DE502006007310D1 (en) | 2010-08-12 |
CN1912163A (en) | 2007-02-14 |
KR20070018678A (en) | 2007-02-14 |
DK1752560T3 (en) | 2010-10-25 |
JP2007051372A (en) | 2007-03-01 |
EP1752560B1 (en) | 2010-06-30 |
JP5052838B2 (en) | 2012-10-17 |
ATE472618T1 (en) | 2010-07-15 |
CN1912163B (en) | 2011-06-08 |
KR101365928B1 (en) | 2014-02-20 |
KR20140003356A (en) | 2014-01-09 |
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