EP1353061B1 - Nozzle for fuel injector - Google Patents
Nozzle for fuel injector Download PDFInfo
- Publication number
- EP1353061B1 EP1353061B1 EP03405171A EP03405171A EP1353061B1 EP 1353061 B1 EP1353061 B1 EP 1353061B1 EP 03405171 A EP03405171 A EP 03405171A EP 03405171 A EP03405171 A EP 03405171A EP 1353061 B1 EP1353061 B1 EP 1353061B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nozzle
- nozzle head
- maximum
- accordance
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000446 fuel Substances 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011651 chromium Substances 0.000 claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 230000007704 transition Effects 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001513 hot isostatic pressing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001347 Stellite Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910000531 Co alloy Inorganic materials 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- -1 Stellite 6 Chemical compound 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 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
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005552 hardfacing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
- F02M61/16—Details not provided for in, or of interest apart from, the apparatus of groups F02M61/02 - F02M61/14
- F02M61/166—Selection of particular materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
- F02M61/16—Details not provided for in, or of interest apart from, the apparatus of groups F02M61/02 - F02M61/14
- F02M61/18—Injection nozzles, e.g. having valve seats; Details of valve member seated ends, not otherwise provided for
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
- F02M61/16—Details not provided for in, or of interest apart from, the apparatus of groups F02M61/02 - F02M61/14
- F02M61/18—Injection nozzles, e.g. having valve seats; Details of valve member seated ends, not otherwise provided for
- F02M61/1806—Injection nozzles, e.g. having valve seats; Details of valve member seated ends, not otherwise provided for characterised by the arrangement of discharge orifices, e.g. orientation or size
- F02M61/182—Discharge orifices being situated in different transversal planes with respect to valve member direction of movement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- 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
- F02B75/00—Other engines
- F02B75/02—Engines characterised by their cycles, e.g. six-stroke
- F02B2075/022—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
- F02B2075/025—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle two
-
- 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
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F7/00—Casings, e.g. crankcases or frames
- F02F2007/0097—Casings, e.g. crankcases or frames for large diesel engines
Definitions
- the invention relates to a nozzle head for a fuel injector according to the preamble of claim 1 and a fuel injector of an internal combustion engine, in particular a large diesel engine.
- the fuel - typically a heavy oil or other diesel fuel - is introduced by means of fuel injection nozzles in the combustion chamber.
- These injectors usually include a partially projecting into the combustion chamber nozzle head, which is also referred to as an atomizer.
- the nozzle head is a wear part, which is subject to a high thermal, mechanical and chemical load collective. Depending on the level of stress, damage to the nozzle head may occur, such as material removal due to corrosion, erosion and / or abrasion, or cracks that can lead to breakup.
- the mechanical loads are also based on the high injection pressure, which can be over a thousand bar. Inside the nozzle head, material losses due to cavitation and / or erosion can occur.
- the thermal loads are based on the high temperatures in the combustion chamber and the enormous temperature changes between the combustion temperature and the temperature of the freshly supplied purge air. Also in the interior of the nozzle head, through which the fuel is introduced, the intermittent injection leads to shock-like temperature changes.
- the Chemical stress on the nozzle head is mainly due to high temperature or hot corrosion. Hot corrosion, which is primarily caused by vanadium, sodium and sulfur contained in the fuel, promotes material degradation and erosion. In particular, the corrosion is the reason that a nozzle head can be unusable after a few thousand hours of operation and must be replaced.
- nozzle heads in large diesel engines usually steels or alloys based on nickel or cobalt, such as Stellite 6, are used. With the cobalt-based alloy Stellite 6, it is now possible to achieve sufficient component service lives for nozzle heads in large diesel engines with regard to erosion, abrasion and cavitation (in particular in the bores of the nozzle head).
- WO 95/24 286 A describes a fuel injector consisting of an aforementioned material.
- WO 95/24 286 A describes a fuel injector consisting of an aforementioned material.
- the development can be expected that in future, even more powerful large diesel engines and the load requirements will continue to increase especially for the nozzle heads.
- a chromium-based alloy which has a nickel content of 30% to 48% and further contains 1.5% -15% tungsten and / or 1% -6.5% molybdenum, the sum of the tungsten and the molybdenum content not exceeding 15% ,
- This alloy is disclosed as hard facing, which is particularly suitable for coating valves in automotive engines.
- the Wolframund / or molybdenum content is essential to give the coating material the necessary strength and hardness.
- the object of the invention is to propose a nozzle head, which is better suited to the high load collective in the large diesel engine and in particular has a high hot corrosion resistance.
- the chromium-based alloy to be used for the nozzle head according to the invention proves to be particularly resistant to corrosion, especially hot corrosion, erosion, abrasion, material loss and cavitation.
- a nozzle head, which is made of such a chromium-based alloy can withstand the high load collective in the large diesel engine very well. Its mechanical strength, resistance to cracking and its long-term resistance to pulsation stress meet the requirements. It has been shown that an operating time of 8,000 to 15,000 operating hours is made possible with a nozzle head according to the invention in a large diesel engine.
- the high chromium content of the inventive nozzle head is of particular importance for the resistance to intensive attacks by high-temperature corrosion, as they typically occur in the combustion chamber of a large diesel engine operated with heavy oil.
- Chromium forms dense and adherent chromium oxide layers on the surface of the nozzle heads, which impart chemical resistance to the material. Due to the high chromium content, chromium can also quickly diffuse from the interior of the nozzle head to the surface of the nozzle head and heal there incurred injuries in the oxide layer.
- the material contains at least one reactive element from the group consisting of the elements lanthanum (La), cerium (Ce), yttrium (Y), hafnium (Hf), scandium (Sc) and the rare earth, wherein the content of each reactive element is at most 5%.
- the reactive element from the group consisting of the elements lanthanum (La), cerium (Ce), yttrium (Y), hafnium (Hf), scandium (Sc) and the rare earth, wherein the content of each reactive element is at most 5%.
- the function of the reactive elements in the material is to positively influence the stability of the chromium oxide layer within itself and its adhesion to the nozzle head. Even small amounts of such reactive elements can significantly improve the oxidation behavior and in particular the adhesion of the oxide layer, especially during thermal cycling.
- the nickel content is at least 45%.
- the material is less brittle and can be better processed or processed.
- the nozzle head according to the invention can withstand the high load collective in the large diesel engine in an outstanding manner and, in particular, has a high hot corrosion resistance.
- each reactive element is at most 1%, in particular at most 0.2%.
- the content of carbon (C) is preferably at most 1%, in particular at most 0.05% and the content of silicon (Si) at most 1%, in particular at most 0.5%.
- the presence of one of the reactive elements in the nozzle head according to the invention usually suffices. Depending on the application, however, it may also be advantageous to produce the nozzle head with several of the reactive elements.
- the nozzle head is preferably made of corresponding metal powder having a main particle size of 10 to 200 microns, especially 40 to 150 microns. By this is meant that the majority of the powder grains have a size of 10 to 200, in particular 40 to 150 micrometers.
- the nozzle head has a longitudinal bore and at least one nozzle hole emanating from the longitudinal bore for introducing fuel into a combustion chamber, wherein the transition from the longitudinal bore to the nozzle hole is rounded, preferably electro-chemically (eluted). By rounding the transition areas, sharp edges in the flow path of the fuel are avoided, whereby the flow conditions are optimized.
- the inventive nozzle head is particularly suitable for a fuel injector for an internal combustion engine, especially a diesel engine.
- a fuel injector for an internal combustion engine especially a diesel engine.
- Particularly suitable is the nozzle head according to the invention or the fuel injection nozzle provided therefor for large diesel engines, for example longitudinally purged two-stroke large diesel engines with crosshead drive or four-stroke large diesel engines.
- Fig. 1 shows a sectional view of a fuel injector of a large diesel engine, especially a two-stroke large diesel engine with longitudinal rinse, which is designated overall by the reference numeral 1.
- the fuel injection nozzle 1 comprises an embodiment of a nozzle head 2 according to the invention, which is fastened to a nozzle body 3.
- the nozzle head 2 - as shown - releasably connected to the nozzle body 3, so that the nozzle head is separately exchangeable, that is, without the entire fuel injector 1 must be replaced.
- the nozzle head 2 has a longitudinal bore 20, and a plurality, for example five, nozzle holes 21, of which in Fig. 1 only two are shown.
- the nozzle holes 21 go out each of the longitudinal bore 20 and extend from there in a radial, slightly inclined downward direction.
- the fuel usually a heavy oil or other diesel fuel, in a conventional manner intermittently adapted to the working cycle of the large diesel engine is injected under high pressure through the longitudinal bore 20 and the nozzle holes 21 in the combustion chamber, not shown.
- the nozzle head 2 is made of a material which is a chromium-based alloy comprising a reactive element.
- a reactive element is a rare earth or a similar metal.
- Particularly suitable are lanthanum (La), cerium (Ce), yttrium (Y), hafnium (Hf), scandium (Sc).
- the material has a high nickel content of 45% to 50% by weight in order to ensure better machinability.
- the nickel content of the alloy is above 45% and as a reactive element lanthanum is included with a weight fraction of less than 0.1%.
- the rest is chromium.
- the material comprises more than one reactive element.
- each reactive element is contained at most 1%, especially at most 0.2% by weight.
- the nozzle head 2 according to the invention is preferably produced by means of a hot isostatic pressing method (HIP: hot isostatic pressing).
- HIP hot isostatic pressing
- the starting materials in this case chromium, nickel and lanthanum as a reactive element - sprayed in a conventional manner to powder.
- the grain size of the powder is in this embodiment, for the most part between 45 and 150 microns.
- the nozzle head 2 is made by mechanical, usually machining methods.
- the longitudinal bore 20 and the nozzle holes 21 are drilled.
- the transition areas (edges) between the longitudinal bore 20 and the nozzle holes 21 are rounded. These edges are preferably electrolytically rounded (eluted).
- the process parameters for hot isostatic pressing can be optimized for the respective application.
- the inventive nozzle head 2 has excellent resistance to hot corrosion and the associated loss of material. It has also grown in a very good way to the other requirements of the thermal, mechanical and chemical load collective in a large diesel engine. With such nozzle heads 2, an operating time of 8000 to 15000 hours can be achieved. Even after such a long period of operation, the nozzle heads have still presented in good condition.
- the nozzle head according to the invention is therefore also suitable for future generations of large diesel engines, which are even more powerful and make even higher demands on the load capacity of the nozzle heads.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Fuel-Injection Apparatus (AREA)
- Powder Metallurgy (AREA)
- Portable Nailing Machines And Staplers (AREA)
Abstract
Description
Die Erfindung betrifft einen Düsenkopf für eine Brennstoffeinspritzdüse gemäss Oberbegriff von Anspruch 1 und eine Brennstoffeinspritzdüse einer Brennkraftmaschine, insbesondere eines Grossdieselmotors.The invention relates to a nozzle head for a fuel injector according to the preamble of claim 1 and a fuel injector of an internal combustion engine, in particular a large diesel engine.
Bei Grossdieselmotoren, die beispielsweise als Antriebsaggregate für Schiffe oder zur Stromerzeugung in Stationäranlagen verwendet werden, wird der Brennstoff - typischerweise ist das ein Schweröl oder ein anderer Dieselbrennstoff - mittels Brennstoffeinspritzdüsen in den Verbrennungsraum eingebracht. Diese Einspritzdüsen umfassen üblicherweise einen teilweise in den Verbrennungsraum hineinragenden Düsenkopf, der auch als Zerstäuber bezeichnet wird. Der Düsenkopf ist ein Verschleissteil, das einem hohen thermischen, mechanischen und chemischen Belastungskollektiv unterliegt. Je nach Grad der Belastung können am Düsenkopf Schäden, beispielsweise Materialabtrag infolge von Korrosion, Erosion und/oder Abrasion auftreten, oder Risse, die bis zum Auseinanderbrechen führen können.In large diesel engines, which are used for example as drive units for ships or for power generation in stationary facilities, the fuel - typically a heavy oil or other diesel fuel - is introduced by means of fuel injection nozzles in the combustion chamber. These injectors usually include a partially projecting into the combustion chamber nozzle head, which is also referred to as an atomizer. The nozzle head is a wear part, which is subject to a high thermal, mechanical and chemical load collective. Depending on the level of stress, damage to the nozzle head may occur, such as material removal due to corrosion, erosion and / or abrasion, or cracks that can lead to breakup.
Die mechanischen Belastungen beruhen auch auf dem hohen Einspritzdruck, der über tausend bar betragen kann. Im Inneren des Düsenkopfs können Materialverluste durch Kavitation und/oder Erosion auftreten. Die thermischen Belastungen beruhen auf den hohen Temperaturen im Brennraum und den enormen Temperaturwechseln zwischen der Verbrennungstemperatur und der Temperatur der frisch zugeführten Spülluft. Auch im Inneren des Düsenkopfs, durch welches der Brennstoff eingebracht wird, führt das intermittierende Einspritzen zu schockartigen Temperaturwechseln. Die chemische Belastung des Düsenkopfs ist hauptsächlich in der Hochtemperatur- oder Heisskorrosion begründet. Die Heisskorrosion, die in erster Linie durch im Brennstoff enthaltenes Vanadium, Natrium und Schwefel verursacht wird, begünstigt die Materialabzehrung und Erosion. Insbesondere die Korrosion ist der Grund dafür, dass ein Düsenkopf bereits nach wenigen tausend Betriebsstunden unbrauchbar sein kann und ersetzt werden muss.The mechanical loads are also based on the high injection pressure, which can be over a thousand bar. Inside the nozzle head, material losses due to cavitation and / or erosion can occur. The thermal loads are based on the high temperatures in the combustion chamber and the enormous temperature changes between the combustion temperature and the temperature of the freshly supplied purge air. Also in the interior of the nozzle head, through which the fuel is introduced, the intermittent injection leads to shock-like temperature changes. The Chemical stress on the nozzle head is mainly due to high temperature or hot corrosion. Hot corrosion, which is primarily caused by vanadium, sodium and sulfur contained in the fuel, promotes material degradation and erosion. In particular, the corrosion is the reason that a nozzle head can be unusable after a few thousand hours of operation and must be replaced.
Als Werkstoff für die Düsenköpfe in Grossdieselmotoren werden heute üblicherweise Stähle oder Legierungen auf Nickel- oder Cobalt-Basis, beispielsweise Stellite 6, verwendet. Mit der Cobalt-Basis-Legierung Stellite 6 lassen sich heute für Düsenköpfe in Grossdieselmotoren ausreichende Bauteilstandzeiten im Hinblick auf Erosion, Abrasion und Kavitation (insbesondere in den Bohrungen des Düsenkopfs) erreichen.
Aus der
Aufgabe der Erfindung ist es, einen Düsenkopf vorzuschlagen, der dem hohen Belastungskollektiv im Grossdieselmotor besser gewachsen ist und insbesondere eine hohe Heisskorrosionsbeständigkeit aufweist.The object of the invention is to propose a nozzle head, which is better suited to the high load collective in the large diesel engine and in particular has a high hot corrosion resistance.
Diese Aufgabe wird erfindungsgemäss durch der Gegenstand gemäss Anspruch 1 gelöst.This object is achieved according to the invention by the subject matter of claim 1.
Die für den erfindungsgemässen Düsenkopf zu verwendende Chrom-Basis-Legierung erweist sich als besonders widerstandsfähig gegen Korrosion, speziell Heisskorrosion, Erosion, Abrasion, Materialverlust und Kavitation. Ein Düsenkopf, der aus einer solchen Chrom-Basis-Legierung gefertigt ist, kann dem hohen Belastungskollektiv im Grossdieselmotor sehr gut widerstehen. Auch seine mechanische Festigkeit, seine Beständigkeit gegen Rissbildung und seine dauerhafte Widerstandsfähigkeit gegen Pulsationsbelastungen genügen den Anforderungen. Es hat sich gezeigt, dass mit einem erfindungsgemässen Düsenkopf in einem Grossdieselmotor eine Betriebsdauer von 8000 bis 15000 Betriebsstunden ermöglicht wird.The chromium-based alloy to be used for the nozzle head according to the invention proves to be particularly resistant to corrosion, especially hot corrosion, erosion, abrasion, material loss and cavitation. A nozzle head, which is made of such a chromium-based alloy, can withstand the high load collective in the large diesel engine very well. Its mechanical strength, resistance to cracking and its long-term resistance to pulsation stress meet the requirements. It has been shown that an operating time of 8,000 to 15,000 operating hours is made possible with a nozzle head according to the invention in a large diesel engine.
Insbesondere der hohe Chrom-Gehalt des erfindungsgemässen Düsenkopfs ist von besonderer Bedeutung für die Resistenz gegenüber intensiven Angriffen durch Hochtemperaturkorrosion, wie sie typischerweise im Verbrennungsraum eines mit Schweröl betriebenen Grossdieselmotors auftreten. Chrom bildet auf der Oberfläche der Düsenköpfe dichte und festhaftende Chromoxidschichten, welche dem Werkstoff eine chemische Beständigkeit verleihen. Bedingt durch den hohen Chrom-Gehalt, kann Chrom zudem rasch aus dem Innern des Düsenkopfs an die Oberfläche des Düsenkopfs diffundieren und dort entstandene Verletzungen in der Oxidschicht ausheilen.In particular, the high chromium content of the inventive nozzle head is of particular importance for the resistance to intensive attacks by high-temperature corrosion, as they typically occur in the combustion chamber of a large diesel engine operated with heavy oil. Chromium forms dense and adherent chromium oxide layers on the surface of the nozzle heads, which impart chemical resistance to the material. Due to the high chromium content, chromium can also quickly diffuse from the interior of the nozzle head to the surface of the nozzle head and heal there incurred injuries in the oxide layer.
Vorzugsweise enthält der Werkstoff mindestens ein reaktives Element aus der Gruppe, die aus den Elementen Lanthan (La), Cer (Ce), Yttrium (Y), Hafnium (Hf), Scandium (Sc) und den Seltenen Erden besteht, wobei der Gehalt an jedem reaktiven Element höchstens 5% beträgt.Preferably, the material contains at least one reactive element from the group consisting of the elements lanthanum (La), cerium (Ce), yttrium (Y), hafnium (Hf), scandium (Sc) and the rare earth, wherein the content of each reactive element is at most 5%.
Die Funktion der reaktiven Elemente in dem Werkstoff ist es, die Stabilität der Chromoxidschicht in sich selbst und ihre Anhaftung an dem Düsenkopf in positiver Weise zu beeinflussen. Schon geringe Mengen solcher reaktiver Elemente können das Oxidationsverhalten und insbesondere das Anhaften der Oxidschicht speziell auch bei Temperaturwechselbelastungen deutlich verbessern.The function of the reactive elements in the material is to positively influence the stability of the chromium oxide layer within itself and its adhesion to the nozzle head. Even small amounts of such reactive elements can significantly improve the oxidation behavior and in particular the adhesion of the oxide layer, especially during thermal cycling.
Im Hinblick auf die mechanisch technologischen Eigenschaften beträgt der Nickel-Gehalt mindestens 45% Durch den dadurch bedingten geringeren Chrom-Gehalt ist der Werkstoff weniger spröde und kann besser verarbeitet bzw. bearbeitet werden.In view of the mechanical technological properties, the nickel content is at least 45%. As a result of the resulting lower chromium content, the material is less brittle and can be better processed or processed.
Es hat sich gezeigt, dass der erfindungsgemässe Düsenkopf dem hohen Belastungskollektiv im Grossdieselmotor in hervorragender Weise widerstehen kann und insbesondere eine hohe Heisskorrosionsbeständigkeit aufweist.It has been found that the nozzle head according to the invention can withstand the high load collective in the large diesel engine in an outstanding manner and, in particular, has a high hot corrosion resistance.
Das Hinzufügen von Komponenten wie beispielsweise Wolfram oder Molybdän, welche die Härte bzw. die Festigkeit erhöhen sollen, ist bei dem erfindungsgemässen Düsenkopf nicht notwendig.The addition of components such as tungsten or molybdenum, which are intended to increase the hardness or strength, is not necessary in the case of the nozzle head according to the invention.
In der Praxis hat es sich als vorteilhaft erwiesen, wenn der Gehalt an jedem reaktiven Element höchstens 1%, insbesondere höchstens 0,2% beträgt. Der Gehalt an Kohlenstoff (C) ist bevorzugt höchstens 1%, insbesondere höchstens 0.05% und der Gehalt an Silizium (Si) höchstens 1%, insbesondere höchstens 0.5%.In practice, it has proved to be advantageous if the content of each reactive element is at most 1%, in particular at most 0.2%. The content of carbon (C) is preferably at most 1%, in particular at most 0.05% and the content of silicon (Si) at most 1%, in particular at most 0.5%.
Üblicherweise reicht das Vorhandensein eines der reaktiven Elemente in dem erfindungsgemässen Düsenkopf aus. Je nach Anwendungsfall kann es jedoch auch vorteilhaft sein, den Düsenkopf mit mehreren der reaktiven Elemente herzustellen.The presence of one of the reactive elements in the nozzle head according to the invention usually suffices. Depending on the application, however, it may also be advantageous to produce the nozzle head with several of the reactive elements.
Für die Eigenschaften eines Werkstoffs, speziell einer Legierung, ist häufig nicht nur seine chemische Zusammensetzung massgebend, sondern auch der Herstellungsprozess. Für den erfindungsgemässen Düsenkopf hat es sich als vorteilhaft erwiesen, wenn er durch ein heissisostatisches Pressverfahren hergestellt wird.For the properties of a material, especially an alloy, often not only its chemical composition is decisive, but also the manufacturing process. For the nozzle head according to the invention, it has proved to be advantageous if it is produced by a hot isostatic pressing method.
Der Düsenkopf wird vorzugsweise hergestellt aus entsprechendem Metallpulver mit einer hauptsächlichen Korngrösse von 10 bis 200 Mikrometern, insbesondere 40 bis 150 Mikrometern. Damit ist gemeint, dass der überwiegende Teil der Pulverkörner eine Grösse von 10 bis 200, insbesondere 40 bis 150 Mikrometern aufweist.The nozzle head is preferably made of corresponding metal powder having a main particle size of 10 to 200 microns, especially 40 to 150 microns. By this is meant that the majority of the powder grains have a size of 10 to 200, in particular 40 to 150 micrometers.
Bei einem bevorzugten Ausführungsbeispiel hat der Düsenkopf eine Längsbohrung und mindestens ein von der Längsbohrung ausgehendes Düsenloch zum Einbringen von Brennstoff in einen Verbrennungsraum, wobei der Übergang von der Längsbohrung zum Düsenloch verrundet ist, vorzugsweise elektro-chemisch (elysiert). Durch das Verrunden der Übergangsbereiche werden scharfe Kanten im Strömungsweg des Brennstoffs vermieden, wodurch die Strömungsbedingungen optimiert werden.In a preferred embodiment, the nozzle head has a longitudinal bore and at least one nozzle hole emanating from the longitudinal bore for introducing fuel into a combustion chamber, wherein the transition from the longitudinal bore to the nozzle hole is rounded, preferably electro-chemically (eluted). By rounding the transition areas, sharp edges in the flow path of the fuel are avoided, whereby the flow conditions are optimized.
Der erfindungsgemässe Düsenkopf eignet sich insbesondere für eine Brennstoffeinspritzdüse für eine Brennkraftmaschine, speziell einen Dieselmotor. Besonders geeignet ist der erfindungsgemässe Düsenkopf bzw. die damit versehene Brennstoffeinspritzdüse für Grossdieselmotoren, beispielsweise längsgespülte Zweitakt-Grossdieselmotoren mit Kreuzkopfantrieb oder Viertakt-Grossdieselmotoren.The inventive nozzle head is particularly suitable for a fuel injector for an internal combustion engine, especially a diesel engine. Particularly suitable is the nozzle head according to the invention or the fuel injection nozzle provided therefor for large diesel engines, for example longitudinally purged two-stroke large diesel engines with crosshead drive or four-stroke large diesel engines.
Weitere vorteilhafte Massnahmen und Ausgestaltungen der Erfindung ergeben sich aus den abhängigen Ansprüchen.Further advantageous measures and embodiments of the invention will become apparent from the dependent claims.
Im Folgenden wird die Erfindung anhand von Ausführungsbeispielen und anhand der Zeichnung näher erläutert. In der schematischen Zeichnung zeigt die einzige Figur:
- Fig. 1:
- eine Schnittdarstellung einer Brennstoffeinspritzdüse mit einem Ausführungsbeispiel eines erfindungsgemässen Düsenkopfs.
- Fig. 1:
- a sectional view of a fuel injector with an embodiment of an inventive nozzle head.
Der Düsenkopf 2 weist eine Längsbohrung 20 auf, sowie mehrere, beispielsweise fünf, Düsenlöcher 21, von denen in
Bei diesem Ausführungsbeispiel besteht der Düsenkopf 2 aus einem Werkstoff, der eine Chrom-Basis-Legierung ist, welche ein reaktives Element umfasst. Als reaktives Element eignet sich eine Seltene Erde oder ein ähnliches Metall. Geeignet sind insbesondere Lanthan (La), Cer (Ce), Yttrium (Y), Hafnium (Hf), Scandium (Sc). Vorzugsweise weist der Werkstoff einen hohen Nickel-Anteil von 45% bis 50% bezogen auf das Gewicht auf, um eine bessere Bearbeitbarkeit zu gewährleisten..In this embodiment, the
Im vorliegenden Ausführungsbeispiel liegt der Nickel-Gehalt der Legierung über 45% und als reaktives Element ist Lanthan mit einem Gewichtsanteil von weniger als 0,1% enthalten. Abgesehen von üblichen Verunreinigung ist der Rest Chrom.In the present embodiment, the nickel content of the alloy is above 45% and as a reactive element lanthanum is included with a weight fraction of less than 0.1%. Apart from usual pollution, the rest is chromium.
Es ist natürlich auch möglich, dass der Werkstoff mehr als ein reaktives Element umfasst. Vorzugsweise ist jedes reaktive Element mit höchstens 1%, speziell höchstens 0,2% bezogen auf das Gewicht enthalten.Of course, it is also possible that the material comprises more than one reactive element. Preferably, each reactive element is contained at most 1%, especially at most 0.2% by weight.
Der erfindungsgemässe Düsenkopf 2 wird vorzugsweise mittels einem heissisostatischen Pressverfahren (HIP: hot isostatic pressing) hergestellt.The
Zur Herstellung werden die Ausgangswerkstoffe - hier also Chrom, Nickel und Lanthan als reaktives Element - in an sich bekannter Weise zu Pulver verdüst. Die Korngrösse des Pulver liegt bei diesem Ausführungsbeispiel grösstenteils zwischen 45 und 150 Mikrometer. Durch heissisostatisches Pressen wird aus dem Pulver ein Rohling beziehungsweise ein Halbzeug, z. B. eine Stange, hergestellt. Aus dem Rohling wird durch mechanische, üblicherweise spanende Bearbeitungsmethoden der Düsenkopf 2 angefertigt. Die Längsbohrung 20 sowie die Düsenlöcher 21 werden gebohrt. Vorzugsweise werden dann die Übergangsbereiche (Kanten) zwischen der Längsbohrung 20 und den Düsenlöchern 21 abgerundet. Diese Kanten werden vorzugsweise elektro-chemisch verrundet (elysiert).To prepare the starting materials - in this case chromium, nickel and lanthanum as a reactive element - sprayed in a conventional manner to powder. The grain size of the powder is in this embodiment, for the most part between 45 and 150 microns. By hot isostatic pressing a blank or a semi-finished product, for. As a rod manufactured. From the blank, the
Die Prozessparameter für das heissisostatische Pressen können für den jeweiligen Anwendungsfall optimiert werden.The process parameters for hot isostatic pressing can be optimized for the respective application.
Der erfindungsgemässe Düsenkopf 2 weist eine ausgezeichnete Beständigkeit gegen Heisskorrosion und den damit verbundenen Materialverlust auf. Er ist auch den anderen Anforderungen des thermischen, mechanischen und chemischen Belastungskollektivs in einem Grossdieselmotor in sehr guter Weise gewachsen. Mit solchen Düsenköpfen 2 lässt sich eine Betriebsdauer von 8000 bis 15000 Stunden erzielen. Selbst nach solch langer Betriebsdauer haben sich die Düsenköpfe noch immer in einem guten Zustand präsentiert.The
Diese enorme Standzeit ist insbesondere unter wirtschaftlichen Aspekten ein grosser Vorteil.This enormous service life is a great advantage especially in economic terms.
Der erfindungsgemässe Düsenkopf eignet sich somit auch für zukünftige Generationen von Grossdieselmotoren, die noch leistungsfähiger sind und noch höhere Anforderungen an die Belastbarkeit der Düsenköpfe stellen.The nozzle head according to the invention is therefore also suitable for future generations of large diesel engines, which are even more powerful and make even higher demands on the load capacity of the nozzle heads.
Claims (8)
- A nozzle head (2) of a fuel injection nozzle (1) of a combustion engine, in particular of a large diesel engine, characterised in that the material of the nozzle head is a chromium based alloy which, except for impurities which usually occur, consists of - in weight percent - at least 45% nickel (Ni), chromium (Cr) in a range of greater than 50% up to and including 55% carbon (C) in a range greater than 0% up to and including 5% silicon (Si)) in a range greater than 0% up to and including 5% and one or more reactive elements in a range greater than 0% up to and including 5%
- The nozzle head (2) in accordance with claim 1, which includes at least one reactive element from the group consisting of the elements lanthanum (La), cerium (Ce), yttrium (Y), hafnium (Hf), scandium (Sc) and the rare earths, with the content of each reactive element amounting to a maximum of 5%.
- The nozzle head (2) in accordance with any one of the preceding claims, wherein the content of each reactive element amounts to a maximum of 1%, in particular a maximum of 0.2%; the content of carbon (C) amounts to a maximum of 1%, in particular a maximum of 0.05%; and the content of silicon (Si) a maximum of 1%, in particular a maximum of 0.5%.
- The nozzle head (2) in accordance with any one of the preceding claims manufactured by a hot isostatic pressing process.
- The nozzle head (2) in accordance with any one of the preceding claims manufactured from a corresponding metal powder having a majority grain size from 10 to 200 micrometers, in particular 40 to 150 micrometers.
- The nozzle head (2) in accordance with any one of the preceding claims, having a longitudinal bore (20) and at least one nozzle aperture starting from the longitudinal bore to introduce fuel into a combustion space, wherein the transition from the longitudinal bore (20) to the nozzle aperture (21) is rounded, preferably electrochemically.
- A fuel injection nozzle (1) for a combustion engine having a nozzle head in accordance with any one of claims 1 to 6.
- A combustion engine, in particular a large diesel engine, having a fuel injection nozzle in accordance with claim 7.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03405171A EP1353061B1 (en) | 2002-04-11 | 2003-03-12 | Nozzle for fuel injector |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02405289 | 2002-04-11 | ||
EP02405289 | 2002-04-11 | ||
EP03405171A EP1353061B1 (en) | 2002-04-11 | 2003-03-12 | Nozzle for fuel injector |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1353061A2 EP1353061A2 (en) | 2003-10-15 |
EP1353061A3 EP1353061A3 (en) | 2006-05-31 |
EP1353061B1 true EP1353061B1 (en) | 2008-03-05 |
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ID=28686034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03405171A Expired - Lifetime EP1353061B1 (en) | 2002-04-11 | 2003-03-12 | Nozzle for fuel injector |
Country Status (8)
Country | Link |
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EP (1) | EP1353061B1 (en) |
JP (1) | JP4870323B2 (en) |
KR (1) | KR100959597B1 (en) |
CN (1) | CN100436625C (en) |
AT (1) | ATE388322T1 (en) |
DE (1) | DE50309291D1 (en) |
DK (1) | DK1353061T3 (en) |
PL (1) | PL199117B1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL1566539T3 (en) * | 2004-02-23 | 2009-05-29 | Waertsilae Nsd Schweiz Ag | Fuel injector |
EP2000550A1 (en) | 2007-06-08 | 2008-12-10 | Wärtsilä Schweiz AG | Material based on a CrNi alloy, semi-finished product, components for a combustion engine and method for manufacturing the material and the semi-finished product |
KR20100101516A (en) | 2009-03-09 | 2010-09-17 | 베르트질레 슈바이츠 악티엔게젤샤프트 | Method for the application of a coating onto a seating surface of a workpiece, as well as a workpiece with a coated seating surface |
CN101694199B (en) * | 2009-08-20 | 2011-05-11 | 余姚市舒春机械有限公司 | Nozzle of low-speed diesel engine |
DE102009046437B4 (en) * | 2009-11-05 | 2018-04-19 | Man Diesel & Turbo Se | Method for processing an injection nozzle |
AT511880B1 (en) * | 2011-09-06 | 2013-12-15 | Bosch Gmbh Robert | WEAR-OPTIMIZED MANUFACTURE OF TAPPY SPRAY HOLES |
CN115324799B (en) * | 2022-06-29 | 2023-06-06 | 中汽研汽车检验中心(天津)有限公司 | Method and device for representing carbon deposition of gasoline engine nozzle |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0676638B2 (en) * | 1986-07-01 | 1994-09-28 | 三菱マテリアル株式会社 | High strength Ni-Cr alloy with excellent corrosion resistance and heat resistance |
JPS6331301A (en) | 1986-07-25 | 1988-02-10 | Sharp Corp | Band-pass filter |
JPH0639095Y2 (en) * | 1988-03-09 | 1994-10-12 | 住友重機械工業株式会社 | Fuel injection nozzle for diesel engine |
EP0452079A1 (en) * | 1990-04-12 | 1991-10-16 | Tosoh Corporation | High chromium-nickel material and process for producing the same |
JPH04358054A (en) * | 1991-06-03 | 1992-12-11 | Kobe Steel Ltd | Powdery material for thermal spraying and surface-coated parts having excellent erosion resistance |
JP3148340B2 (en) * | 1991-08-27 | 2001-03-19 | 福田金属箔粉工業株式会社 | High-toughness chromium-based alloy for hard facing, powder thereof, and engine valve for automobile coated with the alloy |
SG43243A1 (en) * | 1991-12-03 | 1997-10-17 | Advanced Composite Materials | Pressureless sintering of whisker reinforced alumina composites |
JPH05222481A (en) * | 1992-02-07 | 1993-08-31 | Tosoh Corp | New high chromium-nickel mechanical alloy and its production |
DK0569655T3 (en) * | 1992-05-11 | 1996-02-19 | New Sulzer Diesel Ag | Nozzle head for a fuel injection device |
WO1995024286A1 (en) * | 1994-03-10 | 1995-09-14 | Man B & W Diesel A/S | A method of manufacturing a nozzle for a fuel valve, and a nozzle |
DE59409040D1 (en) * | 1994-07-15 | 2000-02-03 | Waertsilae Nsd Schweiz Ag Wint | Nozzle head for a fuel injector |
US6106643A (en) * | 1997-10-14 | 2000-08-22 | Inco Alloys International, Inc. | Hot working high-chromium alloy |
JPH11285890A (en) * | 1998-04-02 | 1999-10-19 | Kubota Corp | High c/high cr-ni based welding rod |
JPH11293376A (en) | 1998-04-14 | 1999-10-26 | Sumitomo Metal Mining Co Ltd | Chromium-base alloy for hearth member of heating furnace |
DE59907093D1 (en) * | 1998-08-27 | 2003-10-30 | Waertsilae Nsd Schweiz Ag | Method of manufacturing a fuel injector and fuel injector |
-
2003
- 2003-03-12 AT AT03405171T patent/ATE388322T1/en not_active IP Right Cessation
- 2003-03-12 DE DE50309291T patent/DE50309291D1/en not_active Expired - Lifetime
- 2003-03-12 EP EP03405171A patent/EP1353061B1/en not_active Expired - Lifetime
- 2003-03-12 DK DK03405171T patent/DK1353061T3/en active
- 2003-03-13 KR KR1020030015814A patent/KR100959597B1/en not_active IP Right Cessation
- 2003-04-09 PL PL359617A patent/PL199117B1/en not_active IP Right Cessation
- 2003-04-10 JP JP2003106188A patent/JP4870323B2/en not_active Expired - Fee Related
- 2003-04-10 CN CNB031105688A patent/CN100436625C/en not_active Expired - Fee Related
Also Published As
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CN1450186A (en) | 2003-10-22 |
KR100959597B1 (en) | 2010-05-27 |
KR20030081020A (en) | 2003-10-17 |
JP4870323B2 (en) | 2012-02-08 |
CN100436625C (en) | 2008-11-26 |
EP1353061A2 (en) | 2003-10-15 |
DE50309291D1 (en) | 2008-04-17 |
ATE388322T1 (en) | 2008-03-15 |
EP1353061A3 (en) | 2006-05-31 |
JP2003301233A (en) | 2003-10-24 |
PL359617A1 (en) | 2003-10-20 |
DK1353061T3 (en) | 2008-06-23 |
PL199117B1 (en) | 2008-08-29 |
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