JP2008180211A - Manufacturing method for combustion engine or turbine parts - Google Patents
Manufacturing method for combustion engine or turbine parts Download PDFInfo
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- JP2008180211A JP2008180211A JP2007272213A JP2007272213A JP2008180211A JP 2008180211 A JP2008180211 A JP 2008180211A JP 2007272213 A JP2007272213 A JP 2007272213A JP 2007272213 A JP2007272213 A JP 2007272213A JP 2008180211 A JP2008180211 A JP 2008180211A
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- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/008—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of engine cylinder parts or of piston parts other than piston rings
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- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/009—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of turbine components other than turbine blades
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/20—Shapes or constructions of valve members, not provided for in preceding subgroups of this group
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- 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
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2301/00—Using particular materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2303/00—Manufacturing of components used in valve arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49229—Prime mover or fluid pump making
- Y10T29/49298—Poppet or I.C. engine valve or valve seat making
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- General Engineering & Computer Science (AREA)
- Powder Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
【課題】本発明は、燃焼エンジン用またはタービン用部品の製造方法、特に、中空弁部品の製造方法に関する。この製造方法によりはじめて、従来の材料に加え粉末状チタン系合金がこれらの部品に加工できる。
【解決手段】この製造方法において、金属粉末および/または金属合金粉末が配合機中で結合剤および必要であれば融剤と混合され、混合物は射出成形により付形され、付形された配合物は化学的に分離され、化学的に分離された配合物は450℃未満の温度で熱的に分離され、化学的、熱的に分離された配合物は上記金属および/または金属合金の溶融温度未満の温度で焼結されて、上記部品が製造される。これらの部品は、従来のように型締付けおよび加力締付け法、さらに溶融結合法により互いに組み合わせることができる。
【選択図】なしThe present invention relates to a method for manufacturing a combustion engine or turbine component, and more particularly to a method for manufacturing a hollow valve component. Only by this manufacturing method, in addition to conventional materials, powdered titanium-based alloys can be processed into these parts.
In this manufacturing method, metal powder and / or metal alloy powder is mixed with a binder and, if necessary, a fluxing agent in a compounding machine, and the mixture is shaped by injection molding, and the shaped compound is shaped. Is chemically separated, the chemically separated formulation is thermally separated at a temperature below 450 ° C., and the chemically and thermally separated formulation is the melting temperature of the metal and / or metal alloy. The part is manufactured by sintering at a temperature below. These parts can be combined with each other by conventional mold clamping and force clamping, and further by melt bonding.
[Selection figure] None
Description
本発明は、燃焼エンジン用またはタービン用部品の製造方法、特に、中空弁部品の製造方法に関する。 The present invention relates to a method for manufacturing a combustion engine component or a turbine component, and more particularly to a method for manufacturing a hollow valve component.
今日、燃焼エンジンは、高い性能と低い燃料消費量を兼備することが期待されている。
燃焼エンジンに用いられるようなガス交換弁は、非常に高い操作温度と機械的応力に耐えることができなければならない。各吸気工程で、入口弁周囲を流れる補給冷ガスで冷却される入口弁は、500℃以上の弁体温度に達する。出口弁は800℃以上の温度に達する。
Today, combustion engines are expected to combine high performance with low fuel consumption.
Gas exchange valves, such as those used in combustion engines, must be able to withstand very high operating temperatures and mechanical stresses. In each intake step, the inlet valve cooled by the supplemental cold gas flowing around the inlet valve reaches a valve body temperature of 500 ° C. or higher. The outlet valve reaches a temperature above 800 ° C.
弁は可動部品なので、適用される駆動力は揺動質量、すなわち、弁、の重量とともに指数関数的に増大する。したがって、機械的強度と熱的強度を喪失せずに重量に関して弁をさらに最適化する必要がある。 Since the valve is a moving part, the applied driving force increases exponentially with the weight of the oscillating mass, ie the valve. Therefore, there is a need to further optimize the valve with respect to weight without losing mechanical and thermal strength.
心棒、弁コーンおよび弁体を持ち、弁コーンと弁体とがキャビティを形成する中空弁は、例えば特許文献1から知られている。そのような中空弁または中空弁部品は現在、熱押出または据込みおよび鍛造により成形されている。材料No.1.4882(X 50 CrMnNiNbN 21 9)、1.4871(X 53 CrMnNiN 21 9)または2.4955(NiFe 25 Cr 20 NbTi)のような耐熱鋼が、主として弁コーンおよび弁体に用いられている。他の材料、特に粉末形チタン系軽量材料は、酸素、窒素および炭素に比べチタンの反応性が高く、材料の脆化を伴うので、上記の方法を用いては中空弁部品に加工できないか、または有利には加工できない。 A hollow valve having a mandrel, a valve cone and a valve body, in which the valve cone and the valve body form a cavity, is known from Patent Document 1, for example. Such hollow valves or hollow valve parts are currently formed by hot extrusion or upsetting and forging. Material No. Heat resistant steels such as 1.4882 (X 50 CrMnNiNbN 21 9), 1.4871 (X 53 CrMnNiN 21 9) or 2.4955 (NiFe 25 Cr 20 NbTi) are mainly used for valve cones and valve bodies. . Other materials, especially powder-type titanium-based lightweight materials, have higher titanium reactivity than oxygen, nitrogen and carbon, and are accompanied by material embrittlement. Or it cannot be processed advantageously.
したがって、本発明の目的は、燃焼エンジン用またはタービン用部品の製造方法、特に、他の材料も有利に加工できる、弁コーンまたは弁体のような中空弁部品の製造方法、を提供することである。 Accordingly, it is an object of the present invention to provide a method for manufacturing a combustion engine or turbine component, particularly a method for manufacturing a hollow valve component such as a valve cone or valve body that can advantageously process other materials. is there.
上記の目的は、燃焼エンジン用またはタービン用部品の製造方法であって、
(a) 金属粉末および/または金属合金粉末が配合機中で結合剤および必要であれば凝集材料と混合され、
(b) 上記混合物が射出成形により付形され、
(c) 付形された配合物が化学的に分離され、
(d) 化学的に分離された配合物が450℃未満の温度で熱的に分離され、
(e) 化学的、熱的に分離された配合物が上記金属および/または金属合金の溶融温度未満の温度で焼結されて、上記部品が製造される、
製造方法により達成される。
The above object is a method for manufacturing a combustion engine or turbine component,
(A) the metal powder and / or metal alloy powder is mixed in a compounding machine with a binder and, if necessary, an agglomerated material;
(B) the mixture is shaped by injection molding;
(C) the shaped formulation is chemically separated;
(D) the chemically separated formulation is thermally separated at a temperature below 450 ° C .;
(E) the chemically and thermally separated blend is sintered at a temperature below the melting temperature of the metal and / or metal alloy to produce the part;
This is achieved by the manufacturing method.
本発明に係る方法では、マルテンサイト系−フェライト系およびオーステナイト系鋼またはニッケル系合金に加え、特にチタン系材料も中空弁部品に有利に加工できるので、既知の中空弁に比べいっそうの重量節減が達成できる。アルミニウムおよび/またはバナジウムを追加成分として含有するチタン合金を用いるのが好ましい。これらの付加的合金成分は各々、合金の全重量に対し2〜10重量%の量で含有されているのが好ましい。 In the method according to the present invention, in addition to martensite-ferrite and austenitic steels or nickel alloys, particularly titanium-based materials can be advantageously processed into hollow valve parts, further weight savings can be achieved compared to known hollow valves. Can be achieved. It is preferable to use a titanium alloy containing aluminum and / or vanadium as an additional component. Each of these additional alloy components is preferably contained in an amount of 2 to 10% by weight relative to the total weight of the alloy.
結合剤は、以下からなる群から選ばれるのが好ましい: ポリアミド類、ポリオキシメチレン、ポリカーボネート、スチレン−アクリロニトリル−共重合体、ポリイミド、天然ワックス類および天然油類、熱硬化性プラスチック類、シアン酸塩類、ポリプロピレン、ポリアセテート、ポリエチレン、エチレン酢酸ビニル、ポリビニルアルコール、ポリ塩化ビニル、ポリスチレン、ポリメチルメタクリレート、アニリン類、鉱油類、水、寒天、グリセロール、ポリビニルブチリル、ポリブチルメタクリレート、セルロース、オレイン酸、フタレート類、パラフィンワックス類、カルナバ蝋、ポリアクリル酸アンモニウム、ステアリン酸ジグリセリドおよびオレイン酸ジグリセリド、グリセリルモノステアレート、イソプロピルチタネート、ステアリン酸リチウム、モノグリセリド類、ホルムアルデヒド、オクタン酸ホスフェート、スルホン酸オレフィン、リン酸エステル類、ステアリン酸、およびこれらの混合物。結合剤の容積割合は、好ましくは60%未満、より好ましくは20〜50%である。 The binder is preferably selected from the group consisting of: polyamides, polyoxymethylene, polycarbonate, styrene-acrylonitrile-copolymer, polyimide, natural waxes and natural oils, thermosetting plastics, cyanic acid Salts, polypropylene, polyacetate, polyethylene, ethylene vinyl acetate, polyvinyl alcohol, polyvinyl chloride, polystyrene, polymethyl methacrylate, anilines, mineral oils, water, agar, glycerol, polyvinyl butyryl, polybutyl methacrylate, cellulose, oleic acid Phthalates, paraffin waxes, carnauba wax, ammonium polyacrylate, stearic acid diglyceride and oleic acid diglyceride, glyceryl monostearate, isopropyl titanate, Lithium phosphate, monoglycerides, formaldehyde, octanoic acid phosphate, sulfonic acid olefins, phosphoric acid esters, stearic acid, and mixtures thereof. The volume ratio of the binder is preferably less than 60%, more preferably 20 to 50%.
配合機における混合は、好ましくは50〜250℃、最も好ましくは90〜150℃の温度で実施する。 The mixing in the blender is preferably carried out at a temperature of 50 to 250 ° C, most preferably 90 to 150 ° C.
射出成形も好ましくは混合物の温度90〜150℃で、好ましくは400〜800バールの圧力で行なう。 Injection molding is also preferably carried out at a mixture temperature of 90 to 150 ° C., preferably at a pressure of 400 to 800 bar.
化学的分離はパラフィン浴中、好ましくはヘキサン浴中で実施するのが好ましい。化学的分離は、好ましくは10〜65℃、より好ましくは30〜50℃の温度で実施する。 The chemical separation is preferably carried out in a paraffin bath, preferably in a hexane bath. The chemical separation is preferably carried out at a temperature of 10 to 65 ° C, more preferably 30 to 50 ° C.
熱的分離は、450℃未満、好ましくは200〜350℃の温度で、好ましくは真空下に、好ましくは2〜20ミリバールの圧力で実施する。 The thermal separation is carried out at a temperature below 450 ° C., preferably 200-350 ° C., preferably under vacuum, preferably at a pressure of 2-20 mbar.
焼結は、好ましくは金属または金属合金の溶融温度の80〜90%で、より好ましくは不活性ガス雰囲気下で実施する。不活性ガスはアルゴンであるのが好ましい。または、焼結は真空下でも実施できる。この場合には、圧力は好ましくは10-3〜10-5ミリバールである。 Sintering is preferably performed at 80 to 90% of the melting temperature of the metal or metal alloy, more preferably in an inert gas atmosphere. The inert gas is preferably argon. Alternatively, sintering can be performed under vacuum. In this case, the pressure is preferably 10 −3 to 10 −5 mbar.
このようにして製造される中空弁部品は、従来のように型締付けおよび加力締付け法、さらに溶融結合法により互いに組み合わせることができる。例えば、弁体と弁コーンとは焼きばめにより組み合わせることができる。弁コーンと弁心棒とは溶融結合法で組み合わせることができる。 The hollow valve parts manufactured in this way can be combined with each other by a conventional mold clamping and force clamping method and further by a melt bonding method. For example, the valve body and the valve cone can be combined by shrink fitting. The valve cone and the valve stem can be combined by melt bonding.
好ましい実施形態:
上述の方法を用いて、6重量%のアルミニウムと4重量%のバナジウムを含有するチタン合金を弁体と弁コーンに加工した。弁コーンと弁体は焼きばめにより組み合わせた。
Preferred embodiments:
Using the method described above, a titanium alloy containing 6 wt% aluminum and 4 wt% vanadium was processed into a valve body and a valve cone. The valve cone and disc were combined by shrink fitting.
Claims (23)
(a) 金属粉末および/または金属合金粉末が配合機中で結合剤および必要であれば凝集材料と混合され、
(b) 上記混合物が射出成形により付形され、
(c) 付形された配合物が化学的に分離され、
(d) 化学的に分離された配合物が450℃未満の温度で熱的に分離され、
(e) 化学的、熱的に分離された配合物が上記金属および/または金属合金の溶融温度未満の温度で焼結されて、上記部品が製造される、
製造方法。 A method for producing a combustion engine or turbine component, comprising:
(A) the metal powder and / or metal alloy powder is mixed in a compounding machine with a binder and, if necessary, an agglomerated material;
(B) the mixture is shaped by injection molding;
(C) the shaped formulation is chemically separated;
(D) the chemically separated formulation is thermally separated at a temperature below 450 ° C .;
(E) the chemically and thermally separated blend is sintered at a temperature below the melting temperature of the metal and / or metal alloy to produce the part;
Production method.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006049844A DE102006049844A1 (en) | 2006-10-20 | 2006-10-20 | Process for the production of components for internal combustion engines or turbines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008180211A true JP2008180211A (en) | 2008-08-07 |
Family
ID=38657272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007272213A Withdrawn JP2008180211A (en) | 2006-10-20 | 2007-10-19 | Manufacturing method for combustion engine or turbine parts |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20080092383A1 (en) |
| EP (1) | EP1925682B1 (en) |
| JP (1) | JP2008180211A (en) |
| CN (1) | CN101413410B (en) |
| AT (1) | ATE457039T1 (en) |
| DE (2) | DE102006049844A1 (en) |
| ES (1) | ES2337302T3 (en) |
| PT (1) | PT1925682E (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897980A (en) * | 2019-02-22 | 2019-06-18 | 北京科技大学 | The powder injection forming method and titanium or titanium alloy product of titanium or Titanium Powder |
| JP2020517830A (en) * | 2017-04-27 | 2020-06-18 | フェデラル−モーグル バルブトレイン ゲーエムベーハーFederal−Mogul Valvetrain Gmbh | Poppet valve and manufacturing method thereof |
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| ES2738003T3 (en) * | 2004-10-15 | 2020-01-17 | Taisei Kogyo Co Ltd | Production process of porous sinter, porous sinter and porous sinter molding material |
| EP2468436B1 (en) * | 2010-12-16 | 2013-04-03 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Method for manufacturing metal casings with structured surfaces |
| KR102172677B1 (en) | 2012-02-24 | 2020-11-02 | 회가나에스 코오포레이션 | Improved lubricant system for use in powder metallurgy |
| CN104117677B (en) * | 2013-04-23 | 2017-02-08 | 昆山广兴电子有限公司 | Manufacturing method of metal fan wheel |
| CN103240418B (en) * | 2013-05-23 | 2014-12-24 | 北京科技大学 | Near-net shaping method for charging turbine with hollow internal structure |
| FR3037514B1 (en) * | 2015-06-16 | 2019-08-09 | Safran Aircraft Engines | METHOD FOR MANUFACTURING A THREE-DIMENSIONAL PIECE FRYED FROM A POWDER AND INSTALLATION FOR CARRYING OUT SAID METHOD |
| CN105624452B (en) * | 2016-01-05 | 2018-04-24 | 南方科技大学 | Method for preparing porous intermetallic compound |
| ITUA20163944A1 (en) | 2016-05-30 | 2017-11-30 | Nuovo Pignone Tecnologie Srl | Process for making a component of a turbomachine, to a component obtainable consequently and turbomachine comprising the same / Process for obtaining a turbomachinery component, a component obtainable from it and a turbomachine which comprises it |
| ES2776887T3 (en) | 2018-02-12 | 2020-08-03 | Helmholtz Zentrum Geesthacht | Method of producing a metal implant |
| CN109108267B (en) * | 2018-08-03 | 2019-12-20 | 深圳市富荣新材料科技有限公司 | Composition, preparation method and application in field of metal injection molding material |
| CN113399667B (en) * | 2021-06-11 | 2022-08-16 | 深圳市泛海统联精密制造股份有限公司 | Titanium alloy metal powder injection molding feed and preparation method thereof |
| CN114472879B (en) * | 2021-12-20 | 2023-04-25 | 中南大学 | A kind of binder for pure titanium powder injection molding and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3120501C2 (en) * | 1981-05-22 | 1983-02-10 | MTU Motoren- und Turbinen-Union München GmbH, 8000 München | "Process and device for the production of molded parts" |
| JPH02274382A (en) * | 1989-04-12 | 1990-11-08 | Nippon Steel Corp | Hard facing method by welding for engine valve |
| US6351258B1 (en) * | 1997-06-30 | 2002-02-26 | Sony Corporation | Switcher system and I/O switching method |
| DE19804053A1 (en) * | 1998-02-03 | 1999-08-05 | Mwp Mahle J Wizemann Pleuco Gm | Lightweight valve |
| DE10336701B4 (en) * | 2003-08-09 | 2006-12-21 | Mtu Aero Engines Gmbh | Process for the production of components |
| DE102004053874A1 (en) * | 2004-11-04 | 2006-05-11 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for producing products from a metallic composite material |
| ATE423941T1 (en) * | 2005-09-20 | 2009-03-15 | Veritas Ag | VALVE DEVICE |
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2006
- 2006-10-20 DE DE102006049844A patent/DE102006049844A1/en not_active Withdrawn
-
2007
- 2007-10-08 DE DE502007002782T patent/DE502007002782D1/en active Active
- 2007-10-08 PT PT07118021T patent/PT1925682E/en unknown
- 2007-10-08 ES ES07118021T patent/ES2337302T3/en active Active
- 2007-10-08 EP EP07118021A patent/EP1925682B1/en not_active Not-in-force
- 2007-10-08 AT AT07118021T patent/ATE457039T1/en active
- 2007-10-09 US US11/869,309 patent/US20080092383A1/en not_active Abandoned
- 2007-10-19 CN CN2007101633815A patent/CN101413410B/en not_active Expired - Fee Related
- 2007-10-19 JP JP2007272213A patent/JP2008180211A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020517830A (en) * | 2017-04-27 | 2020-06-18 | フェデラル−モーグル バルブトレイン ゲーエムベーハーFederal−Mogul Valvetrain Gmbh | Poppet valve and manufacturing method thereof |
| CN109897980A (en) * | 2019-02-22 | 2019-06-18 | 北京科技大学 | The powder injection forming method and titanium or titanium alloy product of titanium or Titanium Powder |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080092383A1 (en) | 2008-04-24 |
| DE102006049844A1 (en) | 2008-04-24 |
| EP1925682B1 (en) | 2010-02-03 |
| EP1925682A1 (en) | 2008-05-28 |
| DE502007002782D1 (en) | 2010-03-25 |
| ATE457039T1 (en) | 2010-02-15 |
| ES2337302T3 (en) | 2010-04-22 |
| CN101413410B (en) | 2012-06-27 |
| PT1925682E (en) | 2010-05-10 |
| CN101413410A (en) | 2009-04-22 |
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