EP2741876B1 - Verfahren zum giessen von monokristallinen metallteilen - Google Patents
Verfahren zum giessen von monokristallinen metallteilen Download PDFInfo
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- EP2741876B1 EP2741876B1 EP12758546.1A EP12758546A EP2741876B1 EP 2741876 B1 EP2741876 B1 EP 2741876B1 EP 12758546 A EP12758546 A EP 12758546A EP 2741876 B1 EP2741876 B1 EP 2741876B1
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- casting
- mold
- core
- cavity
- metal
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- 238000005266 casting Methods 0.000 title claims description 68
- 229910052751 metal Inorganic materials 0.000 title claims description 54
- 239000002184 metal Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 39
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000007704 transition Effects 0.000 claims description 24
- 238000011144 upstream manufacturing Methods 0.000 claims description 13
- 230000000149 penetrating effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910000995 CMSX-10 Inorganic materials 0.000 description 2
- 229910001011 CMSX-4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 210000005045 desmin Anatomy 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
Definitions
- the present invention relates to the field of foundry, and in particular the foundry of monocrystalline metal parts.
- the traditional metal alloys are polycrystalline equiaxes: in the solid state, they form a plurality of grains of substantially identical size, typically of the order of 1 mm, but more or less random orientation.
- the grain boundaries are weak points in a metal part produced from such an alloy.
- the use of additives to reinforce these inter-grain seals has the drawback of reducing the temperature of the melting point, which is particularly disadvantageous when the parts thus produced are intended to be used at high temperature.
- columnar polycrystalline alloys were initially proposed whose grains solidify with a determined orientation. This makes it possible, by orienting the grains in the main load direction of the metal part, to increase the resistance of these parts in a particular direction.
- phase Y has a center face cubic crystal lattice, in which the atoms of nickel, aluminum and / or titanium can occupy any of the positions.
- phase Y ' the atoms of aluminum and / or titanium form a cubic configuration, occupying the eight corners of the cube, whereas nickel atoms occupy the faces of the cube.
- One of these new alloys is the "AM1" nickel alloy jointly developed by SNECMA and the ONERA laboratories, the concluded des Mines de Paris, and IMPHY SA.
- the parts produced in such an alloy can achieve not only particularly high mechanical strength in all axes of effort, but also an improved thermal resistance, since it can dispense with additives intended to bind more strongly between them crystalline grains.
- metal parts produced from such monocrystalline alloys can be advantageously used, for example, in the hot parts of turbines.
- the molten alloy is poured into a cavity of a mold through at least one casting channel in the mold, the mold is unhooked after solidification of the alloy, to release the workpiece, and this is then subjected to a heat treatment, such as for example a quenching in which the metal is first heated, and then cooled rapidly, in order to homogenize the phases Y and Y 'in the single crystal without causing its melting .
- the mechanical shocks to which the parts are subjected after the casting can locally destabilize the crystal lattice of the single crystal. Then, the heat treatment can trigger unwanted recrystallizations in the places thus destabilized, thereby losing the monocrystalline character of the room and introducing weak points therein. Even with great efforts, it is very difficult to avoid mechanical shocks in the handling of molds that can have a mass of several dozen pounds, especially since the shakeout of the mold involves, in itself, mechanical shocks. On the other hand, a limited reduction in the heat treatment temperature, alone, does not substantially prevent these recrystallization phenomena.
- the present invention aims to remedy these disadvantages.
- the invention aims to provide a foundry process that allows to largely limit the recrystallization phenomena following the heat treatment of the parts after solidification of the cast alloy in the mold.
- the heat treatment is performed before operations that can weaken the crystalline structure of the single crystal forming the part. While the person skilled in the art could have thought that the presence of at least some remains of the mold during the heat treatment could affect the efficiency of the latter, it turns out that the heat treatment can be thus advanced without deleterious effects on the part metal and that, on the contrary, this advance makes it possible to avoid untimely recrystallizations during the heat treatment.
- said shake-out of the mold comprises a first hammer-shake step, and a subsequent water-jet shake-out step
- said heat treatment can be advantageously carried out before at least the water-jet shake, which is revealed often be the source of recrystallization phenomena during subsequent heat treatments.
- said casting channel may comprise at least at least one transition zone adjacent to said cavity, with a rounding radius of not less than 0.3 mm between said casting channel and said cavity so that to avoid a pronounced bend in the flow of the molten alloy, bend that could give rise to a zone of recrystallization of the alloy.
- the casting channel may have, in this transition zone, an enlarged section, with respect to an upstream section, in the direction of a main axis of a section of the cavity perpendicular to the pouring channel. More particularly, after casting, this transition zone could form at least one thinner metal film than the upstream casting channel, and more particularly at least one such metal film from each of two opposite sides of the casting channel.
- said transition zone may form, after casting, at least one metal veil adjacent to said core and thinner than the upstream casting channel.
- Each metal web adjacent the core may have an outer edge along a substantially concave line adjacent to a surface of the core.
- the transition zone may form at least one metal veil on each side of said core.
- said metal webs adjacent to the core may have outer edges joining at the ends, so as to surround the core.
- this transition zone makes it possible to fill the cavity substantially simultaneously over its entire width, thus avoiding creating, during the solidification of the alloy, irregularities in the crystal structure of the single crystal. These irregularities could indeed cause, during the heat treatment step, a local recrystallization forming a weak point in the metal part.
- the mold may contain a plurality of cavities, arranged in a cluster, for molding a plurality of metal parts simultaneously.
- the process according to the invention is particularly suitable for the production of certain metal parts, such as turbomachine blades.
- the present invention also relates to metal parts obtained by this method.
- FIG. figure 1 A conventional foundry process, as used for example in the production of turbomachine blades and more particularly of high pressure turbine blades, is illustrated in FIG. figure 1 .
- a ceramic mold 150 is produced, typically by the lost wax process, although other conventional methods may be used alternately.
- This ceramic mold 150 comprises a cluster of cavities 151 connected by casting channels 152 to an orifice 153 outside the mold 150.
- Each cavity 151 is shaped to mold a metal part to be produced.
- the mold 150 also comprises cores 155 penetrating into each of the cavities 151.
- a molten alloy 154 is poured into the orifice 153 to fill the cavities 151 through the channels of casting 152.
- the hammer 150 is initially shaken off, in order to release from the mold 150 the metal parts 156 united in a cluster 157.
- an additional step of water jet shaking is then carried out.
- the individual pieces 156 are cut from the cluster 157.
- the cores 155 are then unchecked from each piece 156 in the next step, and the pieces 156 are finally heat-treated.
- This heat treatment can be, for example, quenching, in which the parts 156 are briefly heated, and then quickly cooled, to harden the alloy parts.
- the alloys that can be used in this process include so-called monocrystalline alloys, which allow the production of parts formed by a single crystal grain or monocrystal.
- the heat treatment the object of which is in fact the homogenization of the phases Y and Y 'in the single crystal, can trigger recrystallization phenomena locally weakening the parts.
- the order of the operations is modified, so as to advance the heat treatment step.
- the first step is also the production of a ceramic mold 250.
- this ceramic mold 250 can also be produced by the lost wax process, or by another alternative method among those known to the person of career.
- this ceramic mold 250 comprises a cluster of cavities 251 connected by channels 252 to an orifice 253 outside the mold 250. Each cavity 251 is also shaped to mold a metal part at produce.
- the mold 250 also comprises cores 255 penetrating into each of the cavities 251.
- a molten alloy 254 is poured into the orifice 253 to fill the cavities 251 through the pouring channels 252.
- the mold 250 is also initially shaken off, in order to release the metal pieces 256 united in a cluster 257 from the mold 250.
- gold proceeds directly to the heat treatment step.
- the metal parts 256 still forming a cluster 257 with still remains of the mold 250, are directly subjected to, for example, quenching, in which the parts 256 are briefly heated, and then quickly cooled.
- these channels 252 may comprise transition zones adjacent to the cavities 251.
- the casting channel 252 widens progressively in the direction of a main axis X of a section S of the cavity 251 in a plane A perpendicular to the pouring channel, so that the radius of rounding between the pouring channel 252 and the cavity 251 is not less than 0.3 mm.
- this transition zone widens on one side and the other of the core 253, as well as on the side opposite the core 253.
- the presence of the transition zone thus makes it possible to distribute the flow of molten alloy substantially throughout the width of the cavity 251, thus avoiding the formation of subsequent recrystallization zones.
- the monocrystalline piece 256 illustrated on the figure 4 is a turbine blade. It is illustrated in the raw state of demoulding, that is to say, with the solidified metal out of the mold release channel 252. This metal thus forms a central rod 275, sails 261, 262 and 263, and a section 276 adjacent to the blade head 265.
- the molten alloy flows from the blade head 265, through the blade root 266, to a casting channel 252 connected to a nozzle. another cavity 251 further downstream.
- the flow of molten alloy thus substantially follows the direction of the main axis Z of the blade.
- the web 261, which extends towards the trailing edge 267 of the blade, has an outer edge 268 with a concave upstream segment and a convex downstream segment.
- this outer edge 268 has a radius of curvature R which evolves only very gradually from the central rod 275 to the enlarged section 276.
- the webs 262 and 263, which extend towards the leading edge 269 dawn on each side of the core 253, have respective outer edges 270,271 substantially concave along the core 253.
- These outer edges 270, 271 are joined by their ends above the core 253 and in front thereof, thus forming two connections 272,273, so as to surround the core 253.
- these sails 262, 263 have radii of curvature R 'and R "on the surfaces adjacent to the outer edges 270, 271 in order to avoid the germination of undesirable metallurgical defects in the vicinity of the core 253.
- the transition surface 277 of the sails 261, 262 and 263 and the stem 275 at the enlarged section 276 is also rounded to prevent germination of such defects.
- nickel monocrystalline alloys such as, in particular, AM1 and AM3 from SNECMA, but also others such as CMSX-2®, CMSX-4®, CMSX- 6 ®, and CMSX-10 ® from CM Group, René® N5 and N6 from General Electric, RR2000 and SRR99 from Rolls-Royce, and PWA 1480, 1484 and 1487 from Pratt & Whitney, among others.
- Table 1 illustrates the compositions of these alloys: ⁇ b> Table 1: Compositions of monocrystalline nickel alloys in mass% ⁇ / b> Alloy Cr Co MB W al Ti Your Nb Re Hf VS B Or CMSX-2 8.0 5.0 0.6 8.0 5.6 1.0 6.0 - - - - Ball CMSX-4 6.5 9.6 0.6 6.4 5.6 1.0 6.5 - 3.0 0.1 - - Ball CMSX-6 10.0 5.0 3.0 - 4.8 4.7 6.0 - - 0.1 - - Ball CMSX-10 2.0 3.0 0.4 5.0 5.7 0.2 8.0 - 6.0 0.03 - - Ball René N5 7.0 8.0 2.0 5.0 6.2 - 7.0 - 3.0 0.2 - - Ball René N6 4.2 12.5 1.4 6.0 5.75 - 7.2 - 5.4 0.15 0.05 0,004 Ball RR2000 10.0 15.0 3.0 - 5.5 4.0 - - - - - Ball S
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Claims (19)
- Verfahren zum Gießen von monokristallinen Metallteilen (256), umfassend wenigstens die Schritte:des Gießens einer geschmolzenen Legierung (254) in einen Hohlraum (251) einer Form (250) durch wenigstens einen Gießkanal (252) in der Form (250),der Wärmebehandlung der Legierung unddes Auspackens der Form (250), unddadurch gekennzeichnet, dass die Wärmebehandlung nach Erstarren der Legierung in der Form (250), aber vor dem Ende des Auspackens durchgeführt wird.
- Gießverfahren nach Anspruch 1, wobei das Auspacken der Form (250) einen ersten Schritt eines Auspackens mit dem Hammer und einen nachfolgenden Schritt eines Auspackens mit Wasserstrahl umfasst, wobei die Wärmebehandlung vor wenigstens dem Wasserstrahl-Auspacken durchgeführt wird.
- Gießverfahren nach einem der vorhergehenden Ansprüche, wobei der Gießkanal (252) wenigstens einen an den Hohlraum (251) angrenzenden Übergangsbereich, mit einem Abrundungsradius von nicht weniger als 0,3 mm zwischen dem Gießkanal (252) und dem Hohlraum (251) umfasst.
- Gießverfahren nach Anspruch 3, wobei der Gießkanal (252) einen Querschnitt aufweist, der gegenüber einem vorgelagerten Querschnitt, in der Richtung einer Hauptachse (X) eines Querschnitts (S) des Hohlraums (251) in einer Ebene (A) senkrecht zu dem Gießkanal (252) erweitert ist.
- Gießverfahren nach Anspruch 4, wobei der Übergangsbereich nach dem Gießen wenigstens einen Metallsteg (261, 262, 263), das feiner als der vorgelagerte Gießkanal (252) ist, bildet.
- Gießverfahren nach Anspruch 5, wobei der Übergangsbereich nach dem Gießen auf einer jeden von zwei entgegengesetzten Seiten des Gießkanals (252) wenigstens einen Metallsteg (261, 262, 263), der feiner als der vorgelagerte Gießkanal (252) ist, bildet.
- Gießverfahren nach einem der Ansprüche 5 oder 6, wobei die Form wenigstens einen Kern (255) umfasst, der in den Hohlraum eindringt und einen an den Gießkanal (252) angrenzenden Raum einnimmt, um einen Hohlraum in dem Metallteil (256) zu bilden, und wobei der Übergangsbereich nach dem Gießen wenigstens einen Metallsteg (262, 263) bildet, der an den Kern (255) angrenzt und feiner als der vorgelagerte Gießkanal (252) ist.
- Gießverfahren nach Anspruch 7, wobei der Übergangsbereich nach dem Gießen wenigstens einen an den Kern (255) angrenzenden Metallsteg (262, 263) auf jeder von zwei entgegengesetzten Seiten des Kerns (255) bildet.
- Verfahren zum Gießen von monokristallinen Metallteilen (256), umfassend wenigstens die Schritte:des Gießens einer geschmolzenen Legierung (254) in einen Hohlraum (251) einer Form (250) durch wenigstens einen Gießkanal (252) in der Form (250),der Wärmebehandlung der Legierung unddes Auspackens der Form (250),dadurch gekennzeichnet, dass der Gießkanal (252) wenigstens einen an den Hohlraum (251) angrenzenden Übergangsbereich mit einem Abrundungsradius von nicht weniger als 0,3 mm zwischen dem Gießkanal (252) und dem Hohlraum (251) umfasst.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach Anspruch 9, wobei der Gießkanal (252) einen Querschnitt aufweist, der gegenüber einem vorgelagerten Querschnitt, in der Richtung einer Hauptachse (X) eines Querschnitts (S) des Hohlraums (251) in einer Ebene (A) senkrecht zu dem Gießkanal (252) erweitert ist.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach Anspruch 10, wobei der Übergangsbereich nach dem Gießen wenigstens einen Metallsteg (261, 262, 263), der feiner als der vorgelagerte Gießkanal (252) ist, bildet.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach Anspruch 11, wobei der Übergangsbereich nach dem Gießen auf einer jeden von zwei entgegengesetzten Seiten des Gießkanals (252) wenigstens einen Metallsteg (261, 262, 263), der feiner als der vorgelagerte Gießkanal (252) ist, bildet.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach einem der Ansprüche 11 oder 12, wobei die Form wenigstens einen Kern (255) umfasst, der in den Hohlraum eindringt und einen an den Gießkanal (252) angrenzenden Raum einnimmt, um einen Hohlraum in dem Metallteil (256) zu bilden, und wobei der Übergangsbereich nach dem Gießen wenigstens einen Metallsteg (262, 263) bildet, der an den Kern (255) angrenzt und feiner als der vorgelagerte Gießkanal (252) ist.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach Anspruch 13, wobei der an den Kern (255) angrenzende Metallsteg (262, 263) einen Außenrand (270, 271) aufweist, der einer im Wesentlichen konkaven, benachbarten Linie auf einer Oberfläche des Kerns (255) folgt.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach einem der Ansprüche 13 oder 14, wobei der Übergangsbereich nach dem Gießen wenigstens einen an den Kern (255) angrenzenden Metallsteg (262, 263) auf jeder von zwei entgegengesetzten Seiten des Kerns (255) bildet.
- Verfahren zum Gießen von monokristallinen Metallteilen (256) nach Anspruch 15, wobei die an den Kern (255) angrenzenden Metallstege (262, 263) Außenränder (270, 271) aufweisen, die an den Enden zusammenlaufen, um den Kern (255) zu umschließen.
- Gießverfahren nach einem der Ansprüche 1 bis 16, wobei das Metallteil (256) eine Schaufel einer Turbomaschine ist.
- Gießverfahren nach einem der Ansprüche 1 bis 17, wobei die Form (250) eine Vielzahl von traubenförmig angeordneten Hohlräumen (251) enthält, um eine Vielzahl von Metallteilen (256) gleichzeitig zu formen.
- Monokristallines Metallteil (256), das durch ein Gießverfahren nach einem der Ansprüche 1 bis 18 hergestellt ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1157264A FR2978927B1 (fr) | 2011-08-09 | 2011-08-09 | Procede de fonderie de pieces metalliques monocristallines |
PCT/FR2012/051852 WO2013021130A1 (fr) | 2011-08-09 | 2012-08-06 | Procede de fonderie de pieces metalliques monocristallines |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2741876A1 EP2741876A1 (de) | 2014-06-18 |
EP2741876B1 true EP2741876B1 (de) | 2015-12-09 |
EP2741876B2 EP2741876B2 (de) | 2018-10-17 |
Family
ID=46832472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP12758546.1A Active EP2741876B2 (de) | 2011-08-09 | 2012-08-06 | Verfahren zum giessen von monokristallinen metallteilen |
Country Status (8)
Country | Link |
---|---|
US (1) | US9731350B2 (de) |
EP (1) | EP2741876B2 (de) |
CN (1) | CN103747896B (de) |
BR (1) | BR112014003169B1 (de) |
CA (1) | CA2844584C (de) |
FR (1) | FR2978927B1 (de) |
RU (1) | RU2605023C2 (de) |
WO (1) | WO2013021130A1 (de) |
Families Citing this family (4)
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US9676028B2 (en) * | 2012-07-06 | 2017-06-13 | Pcc Structurals, Inc. | Method for processing castings |
DE202015003228U1 (de) | 2015-05-05 | 2015-08-19 | Bernd Rothenburg | Magnetischer Bodenverschluss für ein Trinkgefäß, der einen Transponder beinhaltet |
CN109530673A (zh) * | 2019-01-16 | 2019-03-29 | 江苏海金非晶科技有限公司 | 非晶母合金颗粒生产模具及生产工艺 |
CN114515818B (zh) * | 2020-11-18 | 2024-04-26 | 中国航发商用航空发动机有限责任公司 | 一种航空发动机燃烧室涡流器的制造方法及模具 |
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GB8829818D0 (en) * | 1988-12-21 | 1989-02-15 | Ae Turbine Components | Processing of castings |
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EP2024114B1 (de) * | 2006-04-19 | 2018-09-19 | Howmet Corporation | Sequentielles fuellen von giessformen |
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2011
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2012
- 2012-08-06 US US14/237,982 patent/US9731350B2/en active Active
- 2012-08-06 BR BR112014003169-0A patent/BR112014003169B1/pt active IP Right Grant
- 2012-08-06 CA CA2844584A patent/CA2844584C/fr active Active
- 2012-08-06 RU RU2014108855/02A patent/RU2605023C2/ru active
- 2012-08-06 CN CN201280038946.6A patent/CN103747896B/zh active Active
- 2012-08-06 WO PCT/FR2012/051852 patent/WO2013021130A1/fr active Application Filing
- 2012-08-06 EP EP12758546.1A patent/EP2741876B2/de active Active
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Also Published As
Publication number | Publication date |
---|---|
CA2844584C (fr) | 2019-08-27 |
CN103747896A (zh) | 2014-04-23 |
CN103747896B (zh) | 2016-10-19 |
RU2605023C2 (ru) | 2016-12-20 |
US20140193291A1 (en) | 2014-07-10 |
WO2013021130A1 (fr) | 2013-02-14 |
EP2741876B2 (de) | 2018-10-17 |
CA2844584A1 (fr) | 2013-02-14 |
US9731350B2 (en) | 2017-08-15 |
RU2014108855A (ru) | 2015-09-20 |
BR112014003169A2 (pt) | 2017-03-01 |
FR2978927A1 (fr) | 2013-02-15 |
EP2741876A1 (de) | 2014-06-18 |
BR112014003169B1 (pt) | 2018-11-27 |
FR2978927B1 (fr) | 2013-09-27 |
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