WO2017006053A1 - Procede de traitement thermique d'une preforme en poudre en alliage a base de titane - Google Patents
Procede de traitement thermique d'une preforme en poudre en alliage a base de titane Download PDFInfo
- Publication number
- WO2017006053A1 WO2017006053A1 PCT/FR2016/051710 FR2016051710W WO2017006053A1 WO 2017006053 A1 WO2017006053 A1 WO 2017006053A1 FR 2016051710 W FR2016051710 W FR 2016051710W WO 2017006053 A1 WO2017006053 A1 WO 2017006053A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- preform
- titanium
- support
- based alloy
- sintering
- Prior art date
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- 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
- B22F3/003—Apparatus, e.g. furnaces
-
- 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
- B22F3/10—Sintering only
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/12—Travelling or movable supports or containers for the charge
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens, or the like for the charge within the furnace
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens, or the like for the charge within the furnace
- F27D5/0006—Composite supporting structures
- F27D5/0018—Separating elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens, or the like for the charge within the furnace
- F27D5/0062—Shields for the charge
-
- 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
- B22F3/10—Sintering only
- B22F2003/1042—Sintering only with support for articles to be sintered
- B22F2003/1046—Sintering only with support for articles to be sintered with separating means for articles to be sintered
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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
- B22F2203/00—Controlling
- B22F2203/11—Controlling temperature, temperature profile
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
-
- 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
-
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
-
- 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
- B22F5/04—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of turbine blades
-
- 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
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
Definitions
- the present invention relates to the general field of heat treatments of powder preforms.
- the invention applies more particularly, but not exclusively, to the sintering of preforms of three-dimensional parts obtained by shaping a titanium-based alloy powder.
- the sintering of the preform consists of a heat treatment at high temperature (typically the sintering temperature is between 70% and 99% of the melting temperature of the material forming the powder of the preform, or even greater than this melting temperature in the case of a liquid phase sintering), intended to densify the powder in order to obtain a consolidated monobloc part.
- high temperature typically the sintering temperature is between 70% and 99% of the melting temperature of the material forming the powder of the preform, or even greater than this melting temperature in the case of a liquid phase sintering
- titanium-based alloys eg TiAl6V4, TiAl-48-2-2, etc.
- TiAl6V4, TiAl-48-2-2, etc. which are particularly sensitive to oxidation
- the sintering conditions must be carefully controlled to minimize contamination of the alloys.
- the finished part in oxygen. Indeed, the presence of oxygen in the finished part significantly deteriorates its properties and mechanical strength.
- Oxygen sources potentially contaminating the part during sintering have been identified among the following:
- the oxygen present in the sintering tools (such as the plate supporting the preform or the oven itself).
- the main purpose of the present invention is therefore to overcome such drawbacks by proposing a method of heat treatment of a powder piece preform comprising a titanium-based alloy, the process comprising the heat treatment of the preform in an oven at a temperature of predefined temperature, the preform being on a support during the heat treatment.
- the method is characterized in that the support comprises a titanium-based alloy whose titanium mass content is greater than or equal to 45%, or a zirconium-based alloy whose zirconium content by mass is greater than or equal to 95% the support material having a melting temperature above the predefined temperature of the heat treatment, and in that an anti-diffusion barrier is disposed between the preform and the support to prevent the preform from being welded to the support .
- the process according to the invention is notably remarkable in that the support on which the preform is placed makes it possible to reduce the oxygen contamination of the final part following the heat treatment (this heat treatment can be sintering).
- the support since the support comprises a high titanium mass content alloy (typically more than 45%) or a high zirconium mass content alloy (typically more than 95%), it can absorb traces of oxygen in the atmosphere present in the furnace enclosure. Indeed, titanium or zirconium can easily absorb the surrounding oxygen by oxidizing. In addition, the support makes it possible to absorb the oxygen that may have already contaminated the preform. Indeed, titanium and zirconium are more reductive than the titanium oxide (TiO 2 ) formed during the oxidation of titanium present in the preform. Thus, the support acts as an oxygen trap for the oxygen present in the preform.
- a high titanium mass content alloy typically more than 45%
- a high zirconium mass content alloy typically more than 95%)
- the preform is typically disposed on a ceramic tray (for example, zirconia, alumina or yttrine). It has been observed that the ceramic tray is progressively degraded after several sintering cycles. An oxidation-reduction reaction occurs between the ceramic tray and the workpiece, resulting in the reduction of the ceramic of the tray, and the enrichment of the oxygen part.
- a ceramic tray for example, zirconia, alumina or yttrine
- the preform is disposed on the support it is not in contact with other tools present in the oven (such as a sole, or a ceramic tray such as those presented above), which advantageously prevents these tools from contaminating the preform.
- the support acts as a barrier or buffer for oxygen between these tools and the preform.
- the support consists of a material having a melting point higher than the predetermined temperature of the heat treatment (for example the temperature of a sintering stage)
- the plate is plastically deformable, that is to say that it undergoes in particular no irreversible modifications of its structure when it is brought to this temperature. Thus, it can be reused for several heat treatment cycles without deforming.
- the support comprises a titanium-based alloy whose titanium mass content is greater than or equal to 90%, more preferably greater than or equal to 99%.
- the support may comprise a titanium-based alloy selected from the following: T40, T60, TiAl6V4, TiAl-48-2-2.
- the support may comprise a zirconium-based alloy selected from Zircaloy-2, Zircaloy-4.
- the support has a thickness of between 0.1 mm and 20 mm.
- the anti-diffusion barrier comprises alumina or yttrium oxide (Yttrine).
- the plate is etched.
- stripped is meant any treatment intended to erode the upper surface of the support intended to support the preform, such as for example: by polishing, by milling, by sandblasting ... This treatment makes it possible to eliminate the oxide layer which can form on the support when it is in the presence of oxygen (the oxygen of the air for example), but also to increase the reactive surface to capture the oxygen during the heat treatment.
- the heat treatment of the preform may be a sintering of the preform, the preset temperature of the heat treatment being the temperature of a sintering stage.
- FIG. 1 is a schematic sectional view of a support according to the invention positioned in the enclosure of a furnace and surmounted by a preform intended to be heat treated.
- the invention will now be described in its application to sintering a titanium-based alloy powder part preform for the purpose of reducing oxygen contamination of the sintered workpiece.
- the invention is not limited only to the sintering of powder preforms, but can also be implemented in any type of heat treatment requiring protection against oxidation, for example debinding a blank of powder mixed with a binder.
- FIG. 1 very schematically illustrates the enclosure 2 of a furnace 1, used to carry out the high temperature sintering of a preform 3.
- the preform 3 is made by shaping a powder of a titanium-based alloy.
- a titanium-based alloy for example, it is possible to use alloys based on titanium such as: TiAl6V4, Ti-17, Ti-6242, Ti-5553, TiAl-48-2-2, TNMB1, etc.
- the shaping of the powder to make the preform 3 can be done using a method of the type MIM ("Metal Injection Molding"), HIP ("Hot Isostatic Pressing"), by casting powder, by film casting (“Tape Casting”), extrusion, etc.
- MIM Metal Injection Molding
- HIP Hot Isostatic Pressing
- a sole 4 disposed in the enclosure, which can also be integrated in the oven.
- This sole 4 may consist of a molybdenum alloy plate (for example of the TZM type) or graphite. Note that in practice several soles 4 may be present in the sintering chamber. For reasons of simplification, only one sole 4 has been shown.
- a tray 5 of ceramic material may possibly overcome the hearth 4 of the oven.
- This ceramic tray 5 may for example comprise zirconia (Zr0 2 ), alumina (Al 2 O 3 ) or even Yttrine (Y 2 0 3 ).
- a support 6 is arranged on the ceramic plate 5.
- This support 6, here taking the form of a support plate 6, consists of a metal or a metal alloy which has reducing properties with regard to titanium dioxide (TiO 2 ) in particular.
- TiO 2 titanium dioxide
- the support plate 6 then acts as an oxygen trap, not only for the oxygen present in the atmosphere of the chamber 2, but also for the oxygen present in the preform 3 which will be positioned on the support plate 6 and the tools present in the oven.
- this support plate 6 also acts as a barrier for the oxygen present in the ceramic tray 5 and the sole 4, which can no longer reach the preform 3 during sintering.
- the support plate 6 covers as much as possible the ceramic tray 5 or the hearth 4, in order to limit the contamination of oxygen coming from these tools.
- the support plate 6 covers the base of the chamber 2 of the oven 1.
- the thickness e of the support plate 6 may for example be between 0.1 mm and 20 mm.
- Materials which have the required reducing properties may be chosen for example from titanium-based alloys or zirconium-based alloys which have mass contents in these sufficiently high elements.
- a titanium-based alloy for the support plate 6 according to the invention preferably has a titanium mass content greater than or equal to 45%, more preferably a titanium content by mass greater than or equal to 90%, or even more preferably a content of mass of titanium greater than or equal to 99%.
- such an alloy may be selected from the following known alloys: T40, T60, TiAl6V4, TiAl-48-2-2.
- a zirconium-based alloy for the support plate 6 according to the invention preferably has a zirconium content greater than or equal to 95%.
- such an alloy may be selected from the following known alloys: Zircaloy-2, Zircaloy-4.
- the support plate 6 is preferably virtually plastically deformable at the heat treatment temperatures envisaged, which means that its mechanical properties and its shape are not affected by the temperatures to which it will be subjected. In other words, the support plate 6 must be dimensionally stable, it may however undergo slight deformations due to the mass of the part that it supports.
- the melting temperature of the material constituting the support plate 6 is greater than the highest temperature at which it will be subjected during the heat treatment.
- the sintering temperature is generally greater than 1100 ° C.
- the melting temperature of the material constituting the support plate 6 is at least greater than 1100 ° C.
- the support plate 6 it is advantageous to strip the support plate 6 before positioning it in the oven 1. To do this, it can be polished, milled or sanded. This pickling treatment makes it possible to remove any oxide layer that may have formed on the support plate 6 in the open air. In addition, the etching also makes it possible to increase the reactive surface of the support plate 6 to improve the oxygen scavenging.
- the support plate 6 is covered at least in part with an anti-diffusion barrier 7 (for example based on alumina or dytrine), so that to prevent the preform 3 which is then positioned on the support plate 6 does not adhere with it because of the diffusion of the metal elements (by a welding-diffusion phenomenon).
- the anti-diffusion barrier is thus disposed between the support plate 6 and the preform 3.
- the deposition of the anti-diffusion barrier 7 can be done directly by applying a layer of powder by brush or spray from a solution.
- an anti-diffusion barrier similar to that described above may be arranged between the ceramic plate 5 and the support plate 6 (or between the sole plate 4 and the support plate 6, if appropriate) in order to avoid that they adhere to each other.
- sintering of the preform 3 can be carried out.
- the operating conditions for sintering a titanium-based alloy powder preform are known to those skilled in the art. art and will not be described in more detail here.
- the sintering of a powder aerospace turbine engine turbine blade preform is carried out, shaped by a metal injection molding (MIM) process.
- the powder used comprises a Ti-48-2-2-type titanium-based alloy.
- the carrier plate 6 used in this example comprises a TiAl6V4 type titanium-based alloy, and was coated with an anti-Yttrine diffusion barrier (Yttrine) by spray from a solution.
- Yttrine anti-Yttrine diffusion barrier
- the sintering of the preform is carried out at a temperature of between 1380 ° C. and 1445 ° C. for a period of between 2 hours and 10 hours under a neutral atmosphere of argon.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
- Furnace Charging Or Discharging (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112018000280-1A BR112018000280B1 (pt) | 2015-07-06 | 2016-07-06 | Processo para tratamento térmico de uma pré-forma |
JP2018520029A JP6987751B2 (ja) | 2015-07-06 | 2016-07-06 | チタン合金粉末製のプリフォームを熱処理するための方法 |
RU2018104320A RU2711395C2 (ru) | 2015-07-06 | 2016-07-06 | Способ термической обработки заготовки из порошка сплава титана |
US15/741,844 US10967430B2 (en) | 2015-07-06 | 2016-07-06 | Method for heat treating a preform made of titanium alloy powder |
CA2991283A CA2991283C (fr) | 2015-07-06 | 2016-07-06 | Procede de traitement thermique d'une preforme en poudre en alliage a base de titane |
CN201680050001.4A CN108291776B (zh) | 2015-07-06 | 2016-07-06 | 热处理由钛合金粉末制备的预成形体的方法 |
EP16750926.4A EP3320287B1 (fr) | 2015-07-06 | 2016-07-06 | Procédé de traitement thermique d'une préforme en poudre en alliage à base de titane |
US17/193,628 US11440095B2 (en) | 2015-07-06 | 2021-03-05 | Method for heat treating a preform made of titanium alloy powder |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1556375A FR3038622B1 (fr) | 2015-07-06 | 2015-07-06 | Procede de traitement thermique d'une preforme en poudre en alliage a base de titane |
FR1556375 | 2015-07-06 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/741,844 A-371-Of-International US10967430B2 (en) | 2015-07-06 | 2016-07-06 | Method for heat treating a preform made of titanium alloy powder |
US17/193,628 Division US11440095B2 (en) | 2015-07-06 | 2021-03-05 | Method for heat treating a preform made of titanium alloy powder |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017006053A1 true WO2017006053A1 (fr) | 2017-01-12 |
Family
ID=54608670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2016/051710 WO2017006053A1 (fr) | 2015-07-06 | 2016-07-06 | Procede de traitement thermique d'une preforme en poudre en alliage a base de titane |
Country Status (9)
Country | Link |
---|---|
US (2) | US10967430B2 (fr) |
EP (1) | EP3320287B1 (fr) |
JP (2) | JP6987751B2 (fr) |
CN (1) | CN108291776B (fr) |
BR (1) | BR112018000280B1 (fr) |
CA (1) | CA2991283C (fr) |
FR (1) | FR3038622B1 (fr) |
RU (1) | RU2711395C2 (fr) |
WO (1) | WO2017006053A1 (fr) |
Cited By (1)
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WO2020245551A1 (fr) | 2019-06-07 | 2020-12-10 | Safran Aircraft Engines | Procede de fabrication de piece de turbomachine par moulage mim |
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CN208555975U (zh) * | 2018-08-15 | 2019-03-01 | 宁波恒普真空技术有限公司 | 一种石墨料板隔离装置 |
WO2020129049A1 (fr) * | 2018-12-16 | 2020-06-25 | Tritone Technologies Ltd. | Supports destinés à des éléments pendant le déliement et le frittage |
FR3093447B1 (fr) * | 2019-03-07 | 2022-06-10 | Inst De Rech Tech Jules Verne | Procédé de fabrication d’une pièce métallique à base de poudre de titane et/ou d’alliage de titane |
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- 2016-07-06 WO PCT/FR2016/051710 patent/WO2017006053A1/fr active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2020245551A1 (fr) | 2019-06-07 | 2020-12-10 | Safran Aircraft Engines | Procede de fabrication de piece de turbomachine par moulage mim |
FR3096912A1 (fr) | 2019-06-07 | 2020-12-11 | Safran Aircraft Engines | Procédé de fabrication de pièce de turbomachine par moulage MIM |
Also Published As
Publication number | Publication date |
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JP6987751B2 (ja) | 2022-01-05 |
BR112018000280B1 (pt) | 2022-03-03 |
JP2021179011A (ja) | 2021-11-18 |
JP2018529027A (ja) | 2018-10-04 |
US11440095B2 (en) | 2022-09-13 |
CN108291776A (zh) | 2018-07-17 |
JP7119183B2 (ja) | 2022-08-16 |
CA2991283C (fr) | 2023-04-04 |
RU2018104320A3 (fr) | 2019-11-18 |
CA2991283A1 (fr) | 2017-01-12 |
RU2711395C2 (ru) | 2020-01-17 |
US20210187609A1 (en) | 2021-06-24 |
EP3320287A1 (fr) | 2018-05-16 |
US20180193915A1 (en) | 2018-07-12 |
CN108291776B (zh) | 2020-11-17 |
FR3038622B1 (fr) | 2017-08-04 |
FR3038622A1 (fr) | 2017-01-13 |
EP3320287B1 (fr) | 2019-08-28 |
BR112018000280A2 (pt) | 2018-09-04 |
RU2018104320A (ru) | 2019-08-06 |
US10967430B2 (en) | 2021-04-06 |
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