EP3223981A1 - Process for manufacturing three-dimensional parts made of aluminium-titanium alloy - Google Patents

Process for manufacturing three-dimensional parts made of aluminium-titanium alloy

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Publication number
EP3223981A1
EP3223981A1 EP15817955.6A EP15817955A EP3223981A1 EP 3223981 A1 EP3223981 A1 EP 3223981A1 EP 15817955 A EP15817955 A EP 15817955A EP 3223981 A1 EP3223981 A1 EP 3223981A1
Authority
EP
European Patent Office
Prior art keywords
pressure
sintering
powder
sintering step
alloy
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.)
Granted
Application number
EP15817955.6A
Other languages
German (de)
French (fr)
Other versions
EP3223981B1 (en
Inventor
Guillaume Fribourg
Jean-François CASTAGNE
Jean-Claude Bihr
Clément GILLOT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Safran Aircraft Engines SAS
Original Assignee
Safran Aircraft Engines SAS
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Filing date
Publication date
Application filed by Safran Aircraft Engines SAS filed Critical Safran Aircraft Engines SAS
Publication of EP3223981A1 publication Critical patent/EP3223981A1/en
Application granted granted Critical
Publication of EP3223981B1 publication Critical patent/EP3223981B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B22F3/101—Changing atmosphere
    • 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
    • B22F3/1017—Multiple heating or additional 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
    • 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
    • B22F3/16—Both compacting and sintering in successive or repeated 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
    • 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
    • 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
    • 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
    • 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 manufacturing processes of three-dimensional parts based on metal alloys.
  • titanium-based alloys are used for parts intended to be subject to significant thermomechanical stresses and corrosive atmospheres. These alloys can reduce the mass of these parts and their use is therefore advantageous for reasons of cost and / or energy efficiency, as is the case for example in the aeronautical field.
  • the manufacture of titanium-based metal alloy parts has traditionally been carried out using processes including the foundry or electron beam melting technique (EBM).
  • EBM electron beam melting technique
  • the manufacture of pieces of complex geometry, such as a turbomachine blade, is difficult and requires significant processing and machining steps subsequent to the application of the aforementioned manufacturing processes. In particular, the additional machining steps often result in a high scrap rate, which increases production costs.
  • MIM Metal Injection Molding
  • Such a method comprises a step of preparing an injection composition based on metal powder (for example of a metal alloy) and of at least one binder (for example a thermoplastic resin), a step of injection of the injection composition in a cavity of a mold for making a blank of the part, a step of selective removal of the binder present in the blank or debinding, for example using a solvent under a controlled temperature, and a step of sintering the metal powder to densify it.
  • metal powder for example of a metal alloy
  • binder for example a thermoplastic resin
  • the inventors have noticed in tests that the inhomogeneity of the mechanical properties or the relatively high oxidation of the pieces obtained by a traditional MIM process was mainly due to changes in the chemical composition of the alloy occurring during manufacture. of the room. More specifically, the inventors have observed that this modification of the chemistry of the part occurs during the step of sintering the alloy powder and that it is mainly due to the evaporation of additive elements. In addition, most known MIM methods recommend applying a reduced pressure in the sintering chamber, and the evaporation of the additive elements is all the higher as the pressure in the chamber is reduced.
  • the present invention aims at overcoming the drawbacks of the MIM processes of the prior art by proposing a method of manufacturing a three-dimensional sintered part comprising a titanium-based alloy which makes it possible to overcome the undesirable modifications of the chemistry of the alloy and to obtain, therefore, pieces of complex geometry with homogeneous mechanical properties.
  • This object is achieved by a method of manufacturing a three-dimensional sintered piece comprising a titanium-based alloy, the method comprising the following steps:
  • a first step of sintering the powder of the titanium-based alloy the powder being during the first sintering step subjected to a first pressure greater than or equal to 1 mbar in order to obtain a preform of the powder-coated piece; sintered alloy.
  • the control of the pressure during the first sintering step is necessary because it is necessary to ensure the densification of the workpiece at a high temperature, while avoiding a significant change in the chemistry of the preform after the first sintering step. Also, by setting a first pressure greater than or equal to 1 mbar, this first pressure is greater than the saturation vapor pressure of the additive elements at the sintering temperature, which limits their evaporation and therefore the modifications in the chemistry of the the part following the first sintering step.
  • the first pressure may be greater than or equal to 10 mbar.
  • the first pressure can be applied for a period of time for example between 1 hour and 24 hours.
  • the method further comprises after the first sintering step, a second sintering step during which a second pressure is imposed, the second pressure being lower than the first pressure, the duration of application of the second pressure being chosen so that the content
  • the weight of aluminum and / or chromium in a layer of thickness of 200 ⁇ m located on the surface of the preform does not vary by more than 5% in relative value after the second sintering step.
  • the second pressure is less than 1 mbar.
  • the second pressure may be less than or equal to 10 -1 mbar, less than or equal to 10 -2 mbar, or even less than or equal to 10 -3 mbar
  • the second pressure may be applied for a period of less than 5 hours, for example, for example between 10 minutes and 5 hours.
  • the porosity of the preform obtained after the first sintering step is further reduced due to the evacuation of the gas present in the porosity.
  • the conditions of the second sintering stage are optimal for evacuating the gas from the porosity, they are also favorable to the evaporation of the additive elements within the alloy which can cause a change in its chemistry, especially at the surface of the preform. It is therefore desirable to limit the duration of this second sintering step. This limitation of duration is possible in the present invention because the densification of the preform has already been advanced during the first sintering step without affecting its chemistry. The duration of the second sintering step can then be significantly reduced so as not to excessively affect the chemistry of the alloy while being useful for evacuating the gas present in the porosity of the preform and thus improve the densification obtained.
  • the duration of application of the second pressure is determined so that the mass contents of addition elements (such as aluminum and / or chromium) at the surface of the preform do not vary by more than 5% in relative value. following the second sintering step.
  • mass content of an addition element on the surface of the preform By mass content of an addition element on the surface of the preform, the mass proportion of an element in a layer with a thickness of the order of 200 ⁇ m located on the surface of the preform is understood here.
  • mass contents at the surface are determined on samples of the preform before sintering and after sintering by destructive or semi-destructive chemical analyzes, in particular by: plasma torch spectrometry (ICP), energy dispersive analysis (EDX), analysis wavelength dispersive (WDS) or X-ray fluorescence spectrometry (XRF).
  • ICP plasma torch spectrometry
  • EDX energy dispersive analysis
  • WDS analysis wavelength dispersive
  • XRF X-ray fluorescence spectrometry
  • the method further comprises, after the second sintering step, a third sintering step during which a third pressure is imposed, the third pressure being greater at the second pressure, and may for example be greater than or equal to 1 mbar.
  • the third sintering step makes it possible to complete the densification of the part, for example if too many addition elements have evaporated and the desired densification is not reached.
  • the duration of this third step therefore depends on the state of progress of the densification of the preform after the second sintering step.
  • the duration of this third step may be for example between 10 minutes and 10 hours.
  • the invention also relates to the manufacturing method described above in which the manufactured part is a turbomachine blade.
  • the aluminum mass content of the titanium-based alloy powder is greater than 10% before the first sintering step.
  • the titanium-based alloy powder has, before the first sintering step, the mass contents in the following elements: between 32% and 33.5% of aluminum, between 4.5% and 5.1% of niobium and between 2.4% and 2.7% chromium.
  • the titanium-based alloy powder has, before the first sintering step, the mass contents in the following elements: between 28.12% and 29.12% aluminum, between 8.56% and 9.56% of aluminum. niobium, and between 1.84% and 2.84% molybdenum.
  • the titanium-based alloy powder has, before the first sintering stage, the mass contents of the following elements: between 5.4% and 6.6% of aluminum, and between 3.6% and 4.4%. % of vanadium.
  • FIG. 1 is a flowchart representing the main steps of a method according to one embodiment of the invention
  • FIG. 2 is a very schematic view of an injection mold
  • FIG. 3 is a very schematic view of a turbomachine blade that can be manufactured by a process according to the invention.
  • one of the steps of an MIM process consists in injecting under pressure into a cavity of a mold an injection composition comprising a powder of a metal alloy and a binder.
  • the alloy powder may preferably be a titanium aluminum alloy powder.
  • the alloys described above can be used.
  • the powder is preferably in the form of substantially spherical grains.
  • the powder preferably has a grain size (d 90 ) of less than or equal to 150 ⁇ m. In other words, if one considers the distribution of the size of the grains composing the powder, 90% of the grains have a size less than or equal to 150 pm.
  • the binder may, in a manner known per se, comprise a compound chosen from: paraffins, thermoplastic resins, agar gel, cellulose, polyethylene, polyethylene glycol, polypropylene, stearic acid, polyoxymethylene, etc. . and their mixtures.
  • an embodiment of a method according to the invention comprises the following steps.
  • An injection composition is prepared (step E10) from an alloy powder as described above and a binder.
  • the injection composition may typically consist of 50% to 70% by volume of alloy powder and 30% to 50% by volume of binder.
  • the injection composition may first be mixed at a temperature between 150 ° C and 200 ° C in a neutral atmosphere, for example, and will be injected at this temperature.
  • the injection mold 1 generally consists of two parts 14, 16 forming a cavity 12 having the shape of the part to be manufactured.
  • the injection mold advantageously has several injection points 18a, 18b, 18c which allow injection into several parts of the cavity 12 of the mold 1.
  • the injection is carried out at pressures ranging from 400 bars to 800 bars.
  • step E20 The injection is then performed (step E20) in the injection mold 1 which is temperature-controlled, for example between 30 ° C and 70 ° C, so that the injection composition becomes plastic to form a blank of the piece to realize.
  • the blank thus produced is said in a "green state" or plastic.
  • the blank is then demolded (step E30), and optionally machined green (step E40) to remove burrs or cores injection points that could have appeared during demolding.
  • the next step is to selectively remove the binder present in the blank thus formed.
  • step E50 also known as "debinding"
  • step E50 makes it possible to obtain a powder that has the shape of the part to be manufactured from a blank of the part in the green state.
  • the selective removal of the binder may consist in dissolving the binder by treatment with a solvent.
  • the selective removal of the binder can be entirely achieved or finalized thermally. In this case, it can be carried out in a sintering chamber in order not to move the powder between the step of selective removal of the binder present in the blank and the first sintering step.
  • the sintering chamber Prior to the introduction of the powder into the sintering chamber, the sintering chamber was purged and decontaminated by cycles pumping under vacuum, for example under reduced pressure of argon or dihydrogen. Indeed, it is necessary to be in a neutral or reducing atmosphere during sintering to avoid oxidation of the elements present in the alloy.
  • the sintering step (step E60) is carried out in a sintering chamber, in which a sintering temperature is imposed progressively.
  • the sintering temperature is of the order of 80% to 90% of the solidus temperature of the alloy present in the powder to be sintered and ramps of 0.10 ° C / minute at 20 ° C / minute can gradually reach this temperature.
  • a first sintering step (step E601) is carried out by subjecting the powder to a first pressure, with a neutral or reducing atmosphere (under argon or dihydrogen for example), greater than or equal to 1 mbar, for example greater than or equal to 10 mbar.
  • a neutral or reducing atmosphere under argon or dihydrogen for example
  • only the first sintering step is carried out.
  • partial sintering is performed during the first sintering step and then a second sintering step is performed.
  • the preform is subjected to a second pressure, less than the first, which is imposed in the sintering chamber for a determined duration (step E602).
  • This second pressure is intended to evacuate the gas present in the porosity of the preform to increase the densification thereof.
  • the duration of application of the second pressure is limited in order to minimize the surface evaporation of the preform of the additive elements such as aluminum and / or chromium.
  • a gas evacuation treatment present in the porosity is carried out. generated during sintering without significantly affecting the composition of the preform, especially on its surface.
  • evaporation on the surface of the preform evaporation of the additive elements in a layer of characteristic thickness (generally of the order of 200 ⁇ m) on the surface of the preform is meant.
  • the evacuation of the gas present in the porosity will be longer and the densification more limited, but the addition elements will be less evaporation on the surface of the preform.
  • the duration of application of the second pressure will be adapted to minimize the relative variation of the mass content of aluminum and / or chromium at the surface of the preform after the second sintering step preferentially to less than 5%, more preferably less than 3%, more preferably less than 1%.
  • the mass content of aluminum and / or chromium at the surface of the preform preferably does not vary by more than 5% in relative value after the second sintering step, more preferably by 3%, and even more so. preferably 1%.
  • step E603 After the second sintering step, it is possible to perform a third sintering step (step E603) during which a third pressure greater than the second pressure is imposed.
  • This third pressure may for example be greater than or equal to 1 mbar.
  • the preform is cooled by ramps of temperature descent, for example of 0, 1 ° C / minute at 60 ° C / minute, to optimize the microstructure of the part.
  • the final piece is obtained from the preform which has undergone finishing treatments (step E70), known per se, such as hot isostatic pressing to finalize the densification of the part, additional heat treatments to optimize the microstructure, surface treatments by machining or polishing, etc.
  • finishing treatments known per se, such as hot isostatic pressing to finalize the densification of the part, additional heat treatments to optimize the microstructure, surface treatments by machining or polishing, etc.
  • the method of the invention is particularly adapted to the manufacture of a turbine engine blade 2, comprising for example a foot 22, a blade 24 and a head 26, such as that illustrated very schematically in FIG.
  • the first example describes a process for manufacturing a titanium alloy blade 2 of the type TiAI6-V4 by a method according to the invention.
  • TiAl6-V4 a grade 23 titanium alloy having substantially spherical grains is available.
  • binder consisting in particular of paraffin wax, poly (ethylene-vinyl acetate) and stearic acid.
  • the injection composition is carried out (step E10) by mixing the alloy powder with the binder under Argon at a temperature of 120 ° C for 2 hours.
  • the injection composition is injected into the cavity 12 of the injection mold 1 (step E20).
  • the blank of green blade 2 is then demolded (step E30) and machined green (step E40) to remove the burrs due to the injection.
  • the blade blank is placed in a hexane bath at 40 ° C for 10 hours to remove the binder by dissolution (step E50).
  • the step of selective elimination of the binder is continued in a sintering chamber, in which the partially removed blank of the binder has been placed, by carrying out heat treatments to remove the last traces of binder.
  • the sintering step (step E60) is initiated by a rise in temperature in the sintering chamber up to 1350 ° C.
  • step E601 The pressure inside the enclosure is then adjusted to 10 mbar for 2 hours to perform a first sintering step (step E601).
  • the preform is cooled and then extracted from the sintering chamber to undergo conventional finishing treatments (step E70).
  • the second example describes a method of manufacturing a blade 2 made of titanium alloy of the type T ⁇ AI 48-2-2 by another method according to the invention.
  • Table 1 Chemical Composition (in% by Weight) of the Alloy A binder mainly composed of polyethylene and polyethylene glycol is also available.
  • the injection composition is carried out (step E10) by mixing the alloy powder with the binder at a temperature of 170 ° C.
  • the injection composition is injected into the cavity 12 of the injection mold 1 (step E20) regulated at 40 ° C. and in which a vacuum has been evacuated.
  • the blank of green blade 2 is then demolded (step E30) and machined green (step E40) to remove the burrs due to the injection.
  • the blade blank is placed in a 75 ° C water bath for 24 hours to dissolve the binder (step E50).
  • the step of selective removal of the binder is continued in a sintering chamber in which the partially removed blank of the binder has been placed, by carrying out heat treatments to remove the last traces of binder.
  • the sintering step (step E60) is initiated by a rise in temperature in the sintering chamber up to 1410 ° C.
  • the pressure inside the chamber is adjusted to 1 mbar for 6 hours to perform a first sintering step (step E601).
  • a second sintering step is carried out (step E602) by lowering the pressure to 10 "1 mbar in the chamber for 30 minutes.
  • the preform is cooled and then extracted from the sintering chamber to undergo conventional finishing treatments (step E70).

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to a process for manufacturing a sintered three-dimensional part comprising an alloy based on titanium, the process comprising the following steps: the preparation of an injection composition (step E10) comprising a binder and a powder of an alloy based on titanium comprising aluminium and/or chromium as alloying element, the injection (step E20) of the injection composition into a cavity of a mould so as to obtain a blank of the part to be formed, the selective elimination of the binder present in the blank (step E50), a first step of sintering (step E601) of the powder of the alloy based on titanium, the powder being, during the first sintering step, subjected to a first pressure greater than or equal to 1 mbar in order to obtain a preform of the part made of sintered alloy powder, and a second sintering step, carried out after the first sintering step, during which a second pressure is imposed (step E602), the second pressure being lower than the first pressure, the application time of the second pressure being chosen so that the weight content of aluminium and/or of chromium in a 200 μm thick layer located at the surface of the preform does not vary by more than 5% as a relative value following the second sintering step.

Description

Procédé de fabrication de pièces tridimensionnelles en alliage d'aluminium et de titane  Process for manufacturing three-dimensional parts made of aluminum alloy and titanium
Arrière-plan de l'invention Background of the invention
La présente invention se rapporte au domaine général des procédés de fabrication de pièces tridimensionnelles à base d'alliages métalliques. The present invention relates to the general field of manufacturing processes of three-dimensional parts based on metal alloys.
Plus particulièrement, des alliages à base de titane sont utilisés pour des pièces destinées à être soumises à des contraintes thermomécaniques importantes et à des atmosphères corrosives. Ces alliages permettent de réduire la masse de ces pièces et leur emploi est par conséquent avantageux pour des raisons de coût et/ou d'efficacité énergétique, comme c'est le cas par exemple dans le domaine aéronautique.  More particularly, titanium-based alloys are used for parts intended to be subject to significant thermomechanical stresses and corrosive atmospheres. These alloys can reduce the mass of these parts and their use is therefore advantageous for reasons of cost and / or energy efficiency, as is the case for example in the aeronautical field.
La fabrication de pièces en alliage métallique à base de titane se fait traditionnellement par des procédés mettant en œuvre notamment de la fonderie ou la technique de fusion par faisceau électronique ou « Electron Beam Melting » (EBM). La fabrication de pièces de géométrie complexe, comme un aubage de turbomachine, est difficile et nécessite des étapes de traitement et d'usinage importantes postérieurement à l'application des procédés d'élaboration précités. En particulier, les étapes d'usinages supplémentaires entraînent souvent un taux de rebut élevé, ce qui augmente les coûts de production.  The manufacture of titanium-based metal alloy parts has traditionally been carried out using processes including the foundry or electron beam melting technique (EBM). The manufacture of pieces of complex geometry, such as a turbomachine blade, is difficult and requires significant processing and machining steps subsequent to the application of the aforementioned manufacturing processes. In particular, the additional machining steps often result in a high scrap rate, which increases production costs.
Afin de maîtriser ces coûts et d'obtenir une pièce de forme précise nécessitant moins d'usinage après élaboration, il est souhaitable de disposer d'un procédé qui permette de fabriquer des pièces complexes en alliage à base de titane qui ne présentent pas ces inconvénients.  In order to control these costs and to obtain a precisely shaped part requiring less machining after processing, it is desirable to have a process that makes it possible to manufacture complex titanium alloy parts that do not have these disadvantages. .
On connaît le procédé de moulage par injection de métal, ou MIM (« Métal Injection Molding »), qui permet d'obtenir des pièces métalliques de formes précises qui ne nécessitent pas d'usinages lourds et coûteux après leur élaboration.  We know the metal injection molding process, or MIM ("Metal Injection Molding"), which provides metal parts of precise shapes that do not require heavy machining and expensive after their development.
Un tel procédé comprend une étape de préparation d'une composition d'injection à base de poudre métallique (par exemple d'un alliage métallique) et d'au moins un liant (par exemple une résine thermoplastique), une étape d'injection de la composition d'injection dans une cavité d'un moule pour réaliser une ébauche de la pièce, une étape d'élimination sélective du liant présent dans l'ébauche ou déliantage, par exemple en utilisant un solvant sous une température contrôlée, et une étape de frittage de la poudre métallique afin de la densifier. Such a method comprises a step of preparing an injection composition based on metal powder (for example of a metal alloy) and of at least one binder (for example a thermoplastic resin), a step of injection of the injection composition in a cavity of a mold for making a blank of the part, a step of selective removal of the binder present in the blank or debinding, for example using a solvent under a controlled temperature, and a step of sintering the metal powder to densify it.
Cependant, les pièces en alliages à base de titane réalisées par des procédés MIM traditionnels présentent souvent des propriétés mécaniques inhomogènes et une oxydation relativement importante, ce qui réduit leur durée de vie. Objet et résumé de l'invention  However, titanium alloy parts made by traditional MIM processes often have inhomogeneous mechanical properties and relatively high oxidation, which reduces their service life. Object and summary of the invention
Les Inventeurs ont remarqué lors d'essais que l'inhomogénéité des propriétés mécaniques ou l'oxydation relativement importante des pièces obtenues par un procédé MIM traditionnel était principalement due à des modifications de la composition chimique de l'alliage se produisant au cours de la fabrication de la pièce. Plus précisément, les Inventeurs ont observé que cette modification de la chimie de la pièce se produit durant l'étape de frittage de la poudre d'alliage et qu'elle est principalement due à l'évaporation d'éléments d'addition. En outre, la plupart des procédés MIM connus préconisent d'appliquer une pression réduite dans l'enceinte de frittage, et l'évaporation des éléments d'addition est d'autant plus élevée que la pression dans l'enceinte est réduite. The inventors have noticed in tests that the inhomogeneity of the mechanical properties or the relatively high oxidation of the pieces obtained by a traditional MIM process was mainly due to changes in the chemical composition of the alloy occurring during manufacture. of the room. More specifically, the inventors have observed that this modification of the chemistry of the part occurs during the step of sintering the alloy powder and that it is mainly due to the evaporation of additive elements. In addition, most known MIM methods recommend applying a reduced pressure in the sintering chamber, and the evaporation of the additive elements is all the higher as the pressure in the chamber is reduced.
La présente invention vise à s'affranchir des inconvénients des procédés MIM de l'art antérieur en proposant un procédé de fabrication d'une pièce tridimensionnelle frittée comportant un alliage à base de titane qui permet de pallier les modifications indésirables de la chimie de l'alliage et d'obtenir, par conséquent, des pièces de géométrie complexe présentant des propriétés mécaniques homogènes.  The present invention aims at overcoming the drawbacks of the MIM processes of the prior art by proposing a method of manufacturing a three-dimensional sintered part comprising a titanium-based alloy which makes it possible to overcome the undesirable modifications of the chemistry of the alloy and to obtain, therefore, pieces of complex geometry with homogeneous mechanical properties.
Ce but est atteint grâce à un procédé de fabrication d'une pièce tridimensionnelle frittée comportant un alliage à base de titane, le procédé comportant les étapes suivantes :  This object is achieved by a method of manufacturing a three-dimensional sintered piece comprising a titanium-based alloy, the method comprising the following steps:
- préparation d'une composition d'injection comprenant un liant et une poudre d'un alliage à base de titane comportant de l'aluminium et/ou du chrome comme élément d'addition,  preparation of an injection composition comprising a binder and a powder of a titanium-based alloy comprising aluminum and / or chromium as an addition element,
- injection de la composition d'injection dans une cavité d'un moule de manière à obtenir une ébauche de la pièce à former, - élimination sélective du liant présent dans l'ébauche, etinjecting the injection composition into a cavity of a mold so as to obtain a blank of the part to be formed, selective elimination of the binder present in the blank, and
- une première étape de frittage de la poudre de l'alliage à base de titane, la poudre étant durant la première étape de frittage soumise à une première pression supérieure ou égale à 1 mbar afin d'obtenir une préforme de la pièce en poudre d'alliage frittée. a first step of sintering the powder of the titanium-based alloy, the powder being during the first sintering step subjected to a first pressure greater than or equal to 1 mbar in order to obtain a preform of the powder-coated piece; sintered alloy.
Le contrôle de la pression pendant la première étape de frittage est nécessaire car il faut assurer la densification de la pièce à une température élevée, tout en évitant une modification notable de la chimie de la préforme suite à la première étape de frittage. Aussi, en fixant une première pression supérieure ou égale à 1 mbar, cette première pression se trouve supérieure à la pression de vapeur saturante des éléments d'addition à la température de frittage, ce qui limite leur évaporation et donc les modifications de la chimie de la pièce suite à la première étape de frittage.  The control of the pressure during the first sintering step is necessary because it is necessary to ensure the densification of the workpiece at a high temperature, while avoiding a significant change in the chemistry of the preform after the first sintering step. Also, by setting a first pressure greater than or equal to 1 mbar, this first pressure is greater than the saturation vapor pressure of the additive elements at the sintering temperature, which limits their evaporation and therefore the modifications in the chemistry of the the part following the first sintering step.
La première pression peut être supérieure ou égale à 10 mbar. The first pressure may be greater than or equal to 10 mbar.
La première pression peut être appliquée pendant une durée comprise par exemple entre 1 heures et 24 heures. The first pressure can be applied for a period of time for example between 1 hour and 24 hours.
Le procédé comporte en outre après la première étape de frittage, une deuxième étape de frittage durant laquelle une deuxième pression est imposée, la deuxième pression étant inférieure à la première pression, la durée d'application de la deuxième pression étant choisie afin que la teneur massique en aluminium et/ou en chrome dans une couche d'épaisseur de 200 Mm située à la surface de la préforme ne varie pas de plus de 5% en valeur relative suite à la deuxième étape de frittage.  The method further comprises after the first sintering step, a second sintering step during which a second pressure is imposed, the second pressure being lower than the first pressure, the duration of application of the second pressure being chosen so that the content The weight of aluminum and / or chromium in a layer of thickness of 200 μm located on the surface of the preform does not vary by more than 5% in relative value after the second sintering step.
De préférence, la deuxième pression est inférieure à 1 mbar. Preferably, the second pressure is less than 1 mbar.
Par exemple, la deuxième pression peut être inférieure ou égale à 10"1 mbar, inférieure ou égale à 10"2 mbar, voire inférieure ou égale à 10"3 mbar. La deuxième pression peut être appliquée pendant une durée inférieure à 5 heures, par exemple comprise par exemple entre 10 minutes et 5 heures. For example, the second pressure may be less than or equal to 10 -1 mbar, less than or equal to 10 -2 mbar, or even less than or equal to 10 -3 mbar The second pressure may be applied for a period of less than 5 hours, for example, for example between 10 minutes and 5 hours.
Ainsi, en réalisant une telle deuxième étape de frittage dans lequel la deuxième pression appliquée est inférieure à la première pression, on diminue encore la porosité de la préforme obtenue après la première étape de frittage du fait de l'évacuation du gaz présent dans la porosité. Toutefois même si les conditions de la deuxième étape de frittage sont optimales pour évacuer le gaz de la porosité, elles sont aussi favorables à l'évaporation des éléments d'addition au sein de l'alliage qui peut entraîner une modification de sa chimie, notamment en surface de la préforme. Il est donc souhaitable de limiter la durée de cette deuxième étape de frittage. Cette limitation de durée est possible dans la présente invention car la densification de la préforme a déjà été avancée lors de la première étape de frittage sans affecter sa chimie. La durée de la deuxième étape de frittage peut être alors significativement réduite de manière à ne pas affecter outre mesure la chimie de l'alliage tout en étant utile pour évacuer le gaz présent dans la porosité de la préforme et ainsi améliorer la densification obtenue. Thus, by performing such a second sintering step in which the second applied pressure is lower than the first pressure, the porosity of the preform obtained after the first sintering step is further reduced due to the evacuation of the gas present in the porosity. . However, even if the conditions of the second sintering stage are optimal for evacuating the gas from the porosity, they are also favorable to the evaporation of the additive elements within the alloy which can cause a change in its chemistry, especially at the surface of the preform. It is therefore desirable to limit the duration of this second sintering step. This limitation of duration is possible in the present invention because the densification of the preform has already been advanced during the first sintering step without affecting its chemistry. The duration of the second sintering step can then be significantly reduced so as not to excessively affect the chemistry of the alloy while being useful for evacuating the gas present in the porosity of the preform and thus improve the densification obtained.
La durée d'application de la deuxième pression est déterminée pour que les teneurs massiques en éléments d'addition (tels que l'aluminium et/ou le chrome) en surface de la préforme ne varient relativement pas de plus de 5% en valeur relative suite à la deuxième étape de frittage.  The duration of application of the second pressure is determined so that the mass contents of addition elements (such as aluminum and / or chromium) at the surface of the preform do not vary by more than 5% in relative value. following the second sintering step.
On entend ici par teneur massique d'un élément d'addition à la surface de la préforme, la proportion massique d'un élément dans une couche d'épaisseur de l'ordre de 200pm située à la surface de la préforme.  By mass content of an addition element on the surface of the preform, the mass proportion of an element in a layer with a thickness of the order of 200 μm located on the surface of the preform is understood here.
Par variation relative de la teneur massique en un élément donné, on entend la variation relative entre la teneur massique dudit élément avant la première étape de frittage et après la deuxième étape de frittage. Par exemple si la teneur massique en aluminium était de 30% avant la première étape de frittage, et qu'elle est de 28,5% après la deuxième étape de frittage, la variation relative de la teneur massique en aluminium suite aux deux premières étapes frittage est de (30- 28,5)/30=5%.  By relative variation of the mass content in a given element is meant the relative variation between the mass content of said element before the first sintering step and after the second sintering step. For example, if the aluminum content by mass was 30% before the first sintering step, and it is 28.5% after the second sintering step, the relative variation of the aluminum mass content following the first two steps sintering is (30-28.5) / 30 = 5%.
Ces teneurs massiques à la surface sont déterminées sur des échantillons de la préforme avant frittage et après frittage par des analyses chimiques destructives ou semi-destructives, notamment par : spectrométrie par torche à plasma (ICP), analyse dispersive en énergie (EDX), analyse dispersive en longueur d'onde (WDS) ou spectrométrie de fluorescence X (XRF).  These mass contents at the surface are determined on samples of the preform before sintering and after sintering by destructive or semi-destructive chemical analyzes, in particular by: plasma torch spectrometry (ICP), energy dispersive analysis (EDX), analysis wavelength dispersive (WDS) or X-ray fluorescence spectrometry (XRF).
De préférence, le procédé comprend en outre, après la deuxième étape de frittage, une troisième étape de frittage durant laquelle une troisième pression est imposée, la troisième pression étant supérieure à la deuxième pression, et pouvant par exemple être supérieure ou égale à 1 mbar. Preferably, the method further comprises, after the second sintering step, a third sintering step during which a third pressure is imposed, the third pressure being greater at the second pressure, and may for example be greater than or equal to 1 mbar.
La troisième étape de frittage permet de terminer la densification de la pièce, par exemple si trop d'éléments d'addition se sont évaporés et que la densification souhaitée n'est pas atteinte. La durée de cette troisième étape dépend donc de l'état d'avancement de la densification de la préforme à l'issue de la deuxième étape de frittage. La durée de cette troisième étape peut être comprise par exemple entre 10 minutes et 10 heures.  The third sintering step makes it possible to complete the densification of the part, for example if too many addition elements have evaporated and the desired densification is not reached. The duration of this third step therefore depends on the state of progress of the densification of the preform after the second sintering step. The duration of this third step may be for example between 10 minutes and 10 hours.
L'invention vise également le procédé de fabrication décrit précédemment dans lequel la pièce fabriquée est une aube de turbomachine.  The invention also relates to the manufacturing method described above in which the manufactured part is a turbomachine blade.
Selon un aspect de l'invention, la teneur massique en aluminium de la poudre d'alliage à base de titane est supérieure à 10% avant la première étape de frittage.  According to one aspect of the invention, the aluminum mass content of the titanium-based alloy powder is greater than 10% before the first sintering step.
De préférence, la poudre d'alliage à base de titane présente avant la première étape de frittage les teneurs massiques en éléments suivantes : entre 32% et 33,5% d'aluminium, entre 4,5% et 5,1% de niobium, et entre 2,4% et 2,7% de chrome.  Preferably, the titanium-based alloy powder has, before the first sintering step, the mass contents in the following elements: between 32% and 33.5% of aluminum, between 4.5% and 5.1% of niobium and between 2.4% and 2.7% chromium.
Alternativement, la poudre d'alliage à base de titane présente avant la première étape de frittage les teneurs massiques en éléments suivantes : entre 28,12% et 29,12% d'aluminium, entre 8,56% et 9,56% de niobium, et entre 1,84% et 2,84% de molybdène.  Alternatively, the titanium-based alloy powder has, before the first sintering step, the mass contents in the following elements: between 28.12% and 29.12% aluminum, between 8.56% and 9.56% of aluminum. niobium, and between 1.84% and 2.84% molybdenum.
Alternativement encore, la poudre d'alliage à base de titane présente avant la première étape de frittage les teneurs massiques en éléments suivantes : entre 5,4% et 6,6% d'aluminium, et entre 3,6% et 4,4% de vanadium.  Alternatively, the titanium-based alloy powder has, before the first sintering stage, the mass contents of the following elements: between 5.4% and 6.6% of aluminum, and between 3.6% and 4.4%. % of vanadium.
Brève description des dessins Brief description of the drawings
D'autres caractéristiques et avantages de la présente invention ressortiront de la description faite ci-dessous, en référence aux dessins annexés qui en illustrent un exemple de réalisation dépourvu de tout caractère limitatif. Sur les figures : Other features and advantages of the present invention will emerge from the description given below, with reference to the accompanying drawings which illustrate an embodiment having no limiting character. In the figures:
- la figure 1 est un ordinogramme représentant les principales étapes d'un procédé selon un mode de réalisation de l'invention, - la figure 2 est une vue très schématique d'un moule d'injection, et FIG. 1 is a flowchart representing the main steps of a method according to one embodiment of the invention, FIG. 2 is a very schematic view of an injection mold, and
- la figure 3 est une vue très schématique d'une aube de turbomachine pouvant être fabriquée par un procédé selon l'invention.  FIG. 3 is a very schematic view of a turbomachine blade that can be manufactured by a process according to the invention.
Description détaillée de l'invention Detailed description of the invention
L'invention sera à présent décrite dans son application à la fabrication de pièces tridimensionnelles frittées en alliages à base de titane. The invention will now be described in its application to the manufacture of three-dimensional sintered parts made of titanium-based alloys.
De façon bien connue en soi, une des étapes d'un procédé MIM consiste à injecter sous pression dans une cavité d'un moule une composition d'injection comprenant une poudre d'un alliage métallique et un liant.  In a manner well known per se, one of the steps of an MIM process consists in injecting under pressure into a cavity of a mold an injection composition comprising a powder of a metal alloy and a binder.
La poudre d'alliage peut préférentiellement être une poudre d'alliage de titane et d'aluminium. On peut utiliser les alliages décrits ci- dessus.  The alloy powder may preferably be a titanium aluminum alloy powder. The alloys described above can be used.
La poudre est de préférence sous forme de grains sensiblement sphériques. La poudre possède de préférence une taille de grains (d90) inférieure ou égale à 150 pm. En d'autres termes, si l'on considère la distribution de la taille des grains composant la poudre, 90% des grains ont une taille inférieure ou égale à 150 pm. The powder is preferably in the form of substantially spherical grains. The powder preferably has a grain size (d 90 ) of less than or equal to 150 μm. In other words, if one considers the distribution of the size of the grains composing the powder, 90% of the grains have a size less than or equal to 150 pm.
Le liant peut, de façon connue en soi, comporter un composé choisi parmi : les paraffines, les résines thermoplastiques, le gel d'agar, la cellulose, le polyéthylène, le polyéthylène glycol, le polypropylène, l'acide stéarique, polyoxyméthylène, etc. et leurs mélanges.  The binder may, in a manner known per se, comprise a compound chosen from: paraffins, thermoplastic resins, agar gel, cellulose, polyethylene, polyethylene glycol, polypropylene, stearic acid, polyoxymethylene, etc. . and their mixtures.
En référence à la figure 1, un mode de mise en œuvre d'un procédé conforme à l'invention, comprend les étapes suivantes.  Referring to Figure 1, an embodiment of a method according to the invention comprises the following steps.
Une composition d'injection est préparée (étape E10) à partir d'une poudre d'alliage tel que décrit plus haut et d'un liant.  An injection composition is prepared (step E10) from an alloy powder as described above and a binder.
La composition d'injection peut être constituée typiquement de poudre d'alliage entre 50% et 70% en volume, et de 30% à 50% en volume de liant. La composition d'injection peut d'abord être mélangée à une température comprise entre 150°C et 200°C sous atmosphère neutre par exemple, et sera injectée à cette température. The injection composition may typically consist of 50% to 70% by volume of alloy powder and 30% to 50% by volume of binder. The injection composition may first be mixed at a temperature between 150 ° C and 200 ° C in a neutral atmosphere, for example, and will be injected at this temperature.
Comme illustré très schématiquement sur la figure 2, le moule d'injection 1 est généralement constitué de deux parties 14, 16 formant une cavité 12 ayant la forme de la pièce à fabriquer. Le moule d'injection possède avantageusement plusieurs points d'injection 18a, 18b, 18c qui permettent une injection dans plusieurs parties de la cavité 12 du moule 1.  As illustrated very schematically in FIG. 2, the injection mold 1 generally consists of two parts 14, 16 forming a cavity 12 having the shape of the part to be manufactured. The injection mold advantageously has several injection points 18a, 18b, 18c which allow injection into several parts of the cavity 12 of the mold 1.
Typiquement, l'injection est effectuée à des pressions pouvant varier de 400 bars à 800 bars.  Typically, the injection is carried out at pressures ranging from 400 bars to 800 bars.
L'injection est ensuite réalisée (étape E20) dans le moule d'injection 1 qui est régulé en température, entre 30°C et 70°C par exemple, de sorte que la composition d'injection devienne plastique pour former une ébauche de la pièce à réaliser. L'ébauche ainsi réalisée est dite dans un « état vert » ou plastique.  The injection is then performed (step E20) in the injection mold 1 which is temperature-controlled, for example between 30 ° C and 70 ° C, so that the injection composition becomes plastic to form a blank of the piece to realize. The blank thus produced is said in a "green state" or plastic.
Il est avantageux de faire l'injection dans une cavité du moule dans laquelle aura été fait le vide, afin de faciliter l'injection et d'assurer l'homogénéité de l'ébauche qui sera moulée.  It is advantageous to inject into a cavity of the mold in which the vacuum has been made, in order to facilitate the injection and to ensure the homogeneity of the blank to be molded.
L'ébauche est ensuite démoulée (étape E30), et éventuellement usinée à l'état vert (étape E40) pour supprimer les bavures ou les carottes des points d'injection qui auraient pu apparaître lors du démoulage.  The blank is then demolded (step E30), and optionally machined green (step E40) to remove burrs or cores injection points that could have appeared during demolding.
L'étape suivante consiste à éliminer sélectivement le liant présent dans l'ébauche ainsi formée.  The next step is to selectively remove the binder present in the blank thus formed.
L'étape d'élimination sélective du liant (étape E50), aussi appelée « déliantage », permet d'obtenir une poudre qui a la forme de la pièce à fabriquer à partir d'une ébauche de la pièce à l'état vert.  The step of selective elimination of the binder (step E50), also known as "debinding", makes it possible to obtain a powder that has the shape of the part to be manufactured from a blank of the part in the green state.
L'élimination sélective du liant peut consister à dissoudre le liant par traitement par un solvant.  The selective removal of the binder may consist in dissolving the binder by treatment with a solvent.
L'élimination sélective du liant peut être entièrement réalisée ou finalisée par voie thermique. Dans ce cas, elle peut être réalisée dans une enceinte de frittage afin de ne pas déplacer la poudre entre l'étape d'élimination sélective du liant présent dans l'ébauche et la première étape de frittage.  The selective removal of the binder can be entirely achieved or finalized thermally. In this case, it can be carried out in a sintering chamber in order not to move the powder between the step of selective removal of the binder present in the blank and the first sintering step.
Préalablement à l'introduction de la poudre dans l'enceinte de frittage, l'enceinte de frittage a été purgée et décontaminée par des cycles de pompage sous vide, par exemple sous pression réduite d'argon ou de dihydrogène. En effet, il est nécessaire d'être sous atmosphère neutre ou réductrice durant le frittage pour éviter l'oxydation des éléments présents dans l'alliage. Prior to the introduction of the powder into the sintering chamber, the sintering chamber was purged and decontaminated by cycles pumping under vacuum, for example under reduced pressure of argon or dihydrogen. Indeed, it is necessary to be in a neutral or reducing atmosphere during sintering to avoid oxidation of the elements present in the alloy.
On réalise l'étape de frittage (étape E60) dans une enceinte de frittage, dans laquelle une température de frittage est imposée progressivement. De façon connue en soi, la température de frittage est de l'ordre de 80% à 90% de la température de solidus de l'alliage présent dans la poudre à fritter et des rampes de 0,10°C/minute à 20°C/minute permettent d'atteindre progressivement cette température.  The sintering step (step E60) is carried out in a sintering chamber, in which a sintering temperature is imposed progressively. In a manner known per se, the sintering temperature is of the order of 80% to 90% of the solidus temperature of the alloy present in the powder to be sintered and ramps of 0.10 ° C / minute at 20 ° C / minute can gradually reach this temperature.
Conformément à l'invention, une première étape de frittage (étape E601) est réalisée en soumettant la poudre à une première pression, d'atmosphère neutre ou réductrice (sous argon ou dihydrogène par exemple), supérieure ou égale à 1 mbar, par exemple supérieure ou égale à 10 mbar.  According to the invention, a first sintering step (step E601) is carried out by subjecting the powder to a first pressure, with a neutral or reducing atmosphere (under argon or dihydrogen for example), greater than or equal to 1 mbar, for example greater than or equal to 10 mbar.
L'évaporation de composés d'addition tels que le chrome et/ou l'aluminium est négligeable pendant toute la durée de la première étape de frittage dans lequel cette première pression est appliquée. Ainsi, durant cette étape la densification de la préforme est conduite tout en évitant une modification de la chimie de la poudre en surface de la préforme par évaporation des éléments d'addition.  The evaporation of addition compounds such as chromium and / or aluminum is negligible throughout the duration of the first sintering step in which this first pressure is applied. Thus, during this step the densification of the preform is conducted while avoiding a change in the powder chemistry on the surface of the preform by evaporation of the additive elements.
Dans un exemple de réalisation, on ne réalise que la première étape de frittage.  In an exemplary embodiment, only the first sintering step is carried out.
En variante, on réalise un frittage partiel durant la première étape de frittage et on réalise ensuite une deuxième étape de frittage.  Alternatively, partial sintering is performed during the first sintering step and then a second sintering step is performed.
Durant cette deuxième étape de frittage, la préforme est soumise à une deuxième pression, inférieure à la première, qui est imposée dans l'enceinte de frittage pendant une durée déterminée (étape E602).  During this second sintering step, the preform is subjected to a second pressure, less than the first, which is imposed in the sintering chamber for a determined duration (step E602).
Cette deuxième pression a pour but d'évacuer le gaz présent dans la porosité de la préforme pour augmenter la densification de celle- ci. Toutefois, comme expliqué plus haut, la durée d'application de la deuxième pression est limitée afin de minimiser l'évaporation en surface de la préforme des éléments d'addition tels que l'aluminium et/ou le chrome. En d'autres termes, on réalise lors de la deuxième étape de frittage un traitement d'évacuation du gaz présent dans la porosité générée au cours du frittage sans affecter significativement la composition de la préforme, notamment à sa surface. This second pressure is intended to evacuate the gas present in the porosity of the preform to increase the densification thereof. However, as explained above, the duration of application of the second pressure is limited in order to minimize the surface evaporation of the preform of the additive elements such as aluminum and / or chromium. In other words, during the second sintering step, a gas evacuation treatment present in the porosity is carried out. generated during sintering without significantly affecting the composition of the preform, especially on its surface.
Par évaporation en surface de la préforme, on entend évaporation des éléments d'addition dans une couche d'épaisseur caractéristique (généralement de l'ordre de 200μιη) à la surface de la préforme.  By evaporation on the surface of the preform, evaporation of the additive elements in a layer of characteristic thickness (generally of the order of 200 μm) on the surface of the preform is meant.
Par exemple, si une valeur de deuxième pression est choisie très faible, l'évacuation du gaz présent dans la porosité sera plus efficace et la densification plus rapide, mais révaporation des éléments d'addition à la surface de la préforme sera d'autant plus importante.  For example, if a value of second pressure is chosen very low, the evacuation of the gas present in the porosity will be more efficient and the densification faster, but the addition elements will be evaporated on the surface of the preform will be all the more important.
Alternativement, si une valeur de deuxième pression plus élevée est appliquée, l'évacuation du gaz présent dans la porosité sera plus longue et la densification plus limitée, mais révaporation des éléments d'addition à la surface de la préforme sera moindre.  Alternatively, if a higher second pressure value is applied, the evacuation of the gas present in the porosity will be longer and the densification more limited, but the addition elements will be less evaporation on the surface of the preform.
Ainsi, la durée d'application de la deuxième pression sera adaptée pour minimiser la variation relative de la teneur massique en aluminium et/ou en chrome à la surface de la préforme suite à la deuxième étape de frittage préférentiellement à moins de 5%, plus préférentiellement à moins de 3%, encore plus préférentiellement à moins de 1%. En d'autres termes, la teneur massique en aluminium et/ou en chrome à la surface de la préforme ne varie pas préférentiellement de plus de 5% en valeur relative suite à la deuxième étape de frittage, plus préférentiellement de 3%, encore plus préférentiellement de 1%.  Thus, the duration of application of the second pressure will be adapted to minimize the relative variation of the mass content of aluminum and / or chromium at the surface of the preform after the second sintering step preferentially to less than 5%, more preferably less than 3%, more preferably less than 1%. In other words, the mass content of aluminum and / or chromium at the surface of the preform preferably does not vary by more than 5% in relative value after the second sintering step, more preferably by 3%, and even more so. preferably 1%.
Après la deuxième étape de frittage, il est possible de réaliser une troisième étape de frittage (étape E603) durant laquelle une troisième pression supérieure à la deuxième pression est imposée. Cette troisième pression peut par exemple être supérieure ou égale à 1 mbar.  After the second sintering step, it is possible to perform a third sintering step (step E603) during which a third pressure greater than the second pressure is imposed. This third pressure may for example be greater than or equal to 1 mbar.
Après la première étape de frittage (étape E601), ou après la deuxième ou la troisième étape de frittage le cas échéant (étapes E602 et E603), la préforme est refroidie par des rampes de descente en température, par exemple de 0,l°C/minute à 60°C/minute, afin d'optimiser la microstructure de la pièce.  After the first sintering step (step E601), or after the second or third sintering step if necessary (steps E602 and E603), the preform is cooled by ramps of temperature descent, for example of 0, 1 ° C / minute at 60 ° C / minute, to optimize the microstructure of the part.
On obtient la pièce finale à partir de la préforme qui aura subi des traitements de finition (étape E70), connus en soi, tels qu'une compression isostatique à chaud pour finaliser la densification de la pièce, des traitements thermiques supplémentaires pour optimiser la microstructure, des traitements de surface par usinage ou polissage, etc. The final piece is obtained from the preform which has undergone finishing treatments (step E70), known per se, such as hot isostatic pressing to finalize the densification of the part, additional heat treatments to optimize the microstructure, surface treatments by machining or polishing, etc.
Le procédé de l'invention est particulièrement adapté à la fabrication d'une aube 2 de turbomachine, comportant par exemple un pied 22, une pale 24 et une tête 26, comme celle illustrée très schématiquement sur la figure 3.  The method of the invention is particularly adapted to the manufacture of a turbine engine blade 2, comprising for example a foot 22, a blade 24 and a head 26, such as that illustrated very schematically in FIG.
Premier exemple Le premier exemple décrit un procédé de fabrication d'une aube 2 en alliage de titane du type TÏAI6-V4 par un procédé selon l'invention. FIRST EXAMPLE The first example describes a process for manufacturing a titanium alloy blade 2 of the type TiAI6-V4 by a method according to the invention.
On dispose d'abord d'une poudre commerciale d'un l'alliage de titane de grade 23 (TÏAI6-V4) ayant des grains sensiblement sphériques Firstly, a commercial powder of a grade 23 titanium alloy (TiAl6-V4) having substantially spherical grains is available.
On dispose aussi d'un liant constitué notamment de cire de paraffine, de poly(éthylène-acétate de vinyle) et d'acide stéarique.  There is also a binder consisting in particular of paraffin wax, poly (ethylene-vinyl acetate) and stearic acid.
La composition d'injection est réalisée (étape E10) en mélangeant la poudre d'alliage avec le liant sous Argon, à une température de 120°C pendant 2 heures.  The injection composition is carried out (step E10) by mixing the alloy powder with the binder under Argon at a temperature of 120 ° C for 2 hours.
La composition d'injection est injectée dans la cavité 12 du moule d'injection 1 (étape E20).  The injection composition is injected into the cavity 12 of the injection mold 1 (step E20).
L'ébauche de l'aube 2 à l'état vert est ensuite démoulée (étape E30) et usinée à l'état vert (étape E40) pour supprimer les bavures dues à l'injection.  The blank of green blade 2 is then demolded (step E30) and machined green (step E40) to remove the burrs due to the injection.
Puis, l'ébauche de l'aube est placée dans un bain d'hexane à 40°C pendant 10 heures pour éliminer le liant par dissolution (étape E50).  Then, the blade blank is placed in a hexane bath at 40 ° C for 10 hours to remove the binder by dissolution (step E50).
L'étape d'élimination sélective du liant se poursuit dans une enceinte de frittage, dans laquelle aura été placée l'ébauche partiellement éliminée du liant, en effectuant des traitements thermiques pour éliminer les dernières traces de liant.  The step of selective elimination of the binder is continued in a sintering chamber, in which the partially removed blank of the binder has been placed, by carrying out heat treatments to remove the last traces of binder.
L'étape de frittage (étape E60) est amorcée par une montée en température dans l'enceinte de frittage jusqu'à 1350°C.  The sintering step (step E60) is initiated by a rise in temperature in the sintering chamber up to 1350 ° C.
La pression à l'intérieur de l'enceinte est alors ajustée à 10 mbar pendant 2 heures pour réaliser une première étape de frittage (étape E601). La préforme est refroidie puis extraite de l'enceinte de frittage pour subir des traitements de finition classiques (étape E70). The pressure inside the enclosure is then adjusted to 10 mbar for 2 hours to perform a first sintering step (step E601). The preform is cooled and then extracted from the sintering chamber to undergo conventional finishing treatments (step E70).
Deuxième exemple Second example
Le deuxième exemple décrit un procédé de fabrication d'une aube 2 en alliage de titane du type TïAI 48-2-2 par un autre procédé selon l'invention. The second example describes a method of manufacturing a blade 2 made of titanium alloy of the type TïAI 48-2-2 by another method according to the invention.
On dispose d'abord d'une poudre commerciale d'un l'alliage de titane de composition chimique telle que décrite dans le Tableau 1, ayant des grains sensiblement sphériques avec un d90 de 25 Mm. Firstly, a commercial powder of a titanium alloy of chemical composition as described in Table 1, having substantially spherical grains with a d 90 of 25 μm is available.
Tableau 1 - Composition chimique (en % massique) de l'alliage On dispose aussi d'un liant principalement constitué de polyéthylène et de polyéthylène glycol.  Table 1 - Chemical Composition (in% by Weight) of the Alloy A binder mainly composed of polyethylene and polyethylene glycol is also available.
La composition d'injection est réalisée (étape E10) en mélangeant la poudre d'alliage avec le liant, à une température de 170°C.  The injection composition is carried out (step E10) by mixing the alloy powder with the binder at a temperature of 170 ° C.
La composition d'injection est injectée dans la cavité 12 du moule d'injection 1 (étape E20) régulé à 40°C et dans laquelle on a fait le vide.  The injection composition is injected into the cavity 12 of the injection mold 1 (step E20) regulated at 40 ° C. and in which a vacuum has been evacuated.
L'ébauche de l'aube 2 à l'état vert est ensuite démoulée (étape E30) et usinée à l'état vert (étape E40) pour supprimer les bavures dues à l'injection.  The blank of green blade 2 is then demolded (step E30) and machined green (step E40) to remove the burrs due to the injection.
Puis, l'ébauche de l'aube est placée dans un bain d'eau à 75°C pendant 24 heures pour éliminer le liant par dissolution (étape E50).  Then, the blade blank is placed in a 75 ° C water bath for 24 hours to dissolve the binder (step E50).
L'étape d'élimination sélective du liant se poursuit dans une enceinte de frittage dans laquelle aura été placée l'ébauche partiellement éliminée du liant, en effectuant des traitements thermiques pour éliminer les dernières traces de liant.  The step of selective removal of the binder is continued in a sintering chamber in which the partially removed blank of the binder has been placed, by carrying out heat treatments to remove the last traces of binder.
L'étape de frittage (étape E60) est amorcée par une montée en température dans l'enceinte de frittage jusqu'à 1410°C. La pression à l'intérieur de l'enceinte est ajustée à 1 mbar pendant 6 heures pour réaliser une première étape de frittage (étape E601). The sintering step (step E60) is initiated by a rise in temperature in the sintering chamber up to 1410 ° C. The pressure inside the chamber is adjusted to 1 mbar for 6 hours to perform a first sintering step (step E601).
Après la première étape de frittage, une deuxième étape de frittage est réalisée (étape E602) en abaissant la pression à 10"1 mbar dans l'enceinte pendant 30 minutes. After the first sintering step, a second sintering step is carried out (step E602) by lowering the pressure to 10 "1 mbar in the chamber for 30 minutes.
La préforme est refroidie puis extraite de l'enceinte de frittage pour subir des traitements de finition classiques (étape E70).  The preform is cooled and then extracted from the sintering chamber to undergo conventional finishing treatments (step E70).

Claims

REVENDICATIONS
1. Procédé de fabrication d'une pièce tridimensionnelle frittée comportant un alliage à base de titane, le procédé comportant les étapes suivantes : A method of manufacturing a three-dimensional sintered piece comprising a titanium-based alloy, the method comprising the following steps:
- préparation d'une composition d'injection comprenant un liant et une poudre d'un alliage à base de titane comportant de l'aluminium et/ou du chrome comme élément d'addition (étape E10),  preparation of an injection composition comprising a binder and a powder of a titanium-based alloy comprising aluminum and / or chromium as addition element (step E10),
- injection de la composition d'injection dans une cavité (12) d'un moule (1) de manière à obtenir une ébauche de la pièce à former injecting the injection composition into a cavity (12) of a mold (1) so as to obtain a blank of the part to be formed
(étape E20), (step E20),
- élimination sélective du liant présent dans l'ébauche (étape E50),  selective removal of the binder present in the blank (step E50),
- une première étape de frittage de la poudre de l'alliage à base de titane (étape E601), la poudre étant durant la première étape de frittage soumise à une première pression supérieure ou égale à 1 mbar afin d'obtenir une préforme de la pièce en poudre d'alliage frittée, et  a first step of sintering the powder of the titanium-based alloy (step E601), the powder being during the first sintering step subjected to a first pressure greater than or equal to 1 mbar in order to obtain a preform of the powder piece of sintered alloy, and
- une deuxième étape de frittage, effectuée après la première étape de frittage, durant laquelle une deuxième pression est imposée (étape E602), la deuxième pression étant inférieure à la première pression, la durée d'application de la deuxième pression étant choisie afin que la teneur massique en aluminium et/ou en chrome dans une couche d'épaisseur de 200 pm située à la surface de la préforme ne varie pas de plus de 5% en valeur relative suite à la deuxième étape de frittage.  a second sintering step, performed after the first sintering step, during which a second pressure is imposed (step E602), the second pressure being lower than the first pressure, the duration of application of the second pressure being chosen so that the mass content of aluminum and / or chromium in a layer of thickness of 200 μm located on the surface of the preform does not vary by more than 5% in relative value following the second sintering step.
2. Procédé selon la revendication 1, dans lequel la deuxième pression est inférieure à 1 mbar. 2. The method of claim 1, wherein the second pressure is less than 1 mbar.
3. Procédé selon l'une quelconque des revendications 1 et 2, comportant en outre, après la deuxième étape de frittage, une troisième étape de frittage durant laquelle une troisième pression est imposée (étape E603), la troisième pression étant supérieure à la deuxième pression. 3. Method according to any one of claims 1 and 2, further comprising, after the second sintering step, a third sintering step during which a third pressure is imposed (step E603), the third pressure being greater than the second pressure.
4. Procédé selon la revendication 3, dans lequel la troisième pression est supérieure ou égale à 1 mbar. 4. The method of claim 3, wherein the third pressure is greater than or equal to 1 mbar.
5. Procédé selon l'une quelconque des revendications 1 à 4 dans lequel la pièce obtenue est une aube (2) de turbomachine. 5. Method according to any one of claims 1 to 4 wherein the part obtained is a blade (2) of a turbomachine.
6. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel la teneur massique en aluminium de la poudre d'alliage est supérieure à 10% avant la première étape de frittage. 6. Method according to any one of claims 1 to 5 wherein the aluminum mass content of the alloy powder is greater than 10% before the first sintering step.
7. Procédé selon l'une quelconque des revendications 1 à 6 dans lequel la poudre d'alliage présente avant la première étape de frittage les teneurs massiques en éléments suivantes : 7. Method according to any one of claims 1 to 6 wherein the alloy powder has before the first sintering step the mass contents of the following elements:
entre 32% et 33,5% d'aluminium,  between 32% and 33.5% aluminum,
entre 4,5% et 5,1% de niobium, et  between 4.5% and 5.1% of niobium, and
entre 2,4% et 2,7% de chrome.  between 2.4% and 2.7% chromium.
8. Procédé selon l'une quelconque des revendications 1 à 6 dans lequel la poudre d'alliage présente avant la première étape de frittage les teneurs massiques en éléments suivantes : 8. Method according to any one of claims 1 to 6 wherein the alloy powder has before the first sintering step the mass contents of the following elements:
entre 28,12% et 29,12% d'aluminium,  between 28.12% and 29.12% aluminum,
entre 8,56% et 9,56% de niobium, et  between 8.56% and 9.56% of niobium, and
entre 1,84% et 2,84% de molybdène.  between 1.84% and 2.84% molybdenum.
9. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel la poudre d'alliage présente avant la première étape de frittage les teneurs massiques en éléments suivantes : 9. Method according to any one of claims 1 to 5 wherein the alloy powder has before the first sintering step the mass contents of the following elements:
entre 5,4% et 6,6% d'aluminium, et  between 5.4% and 6.6% aluminum, and
entre 3,6% et 4,4% de vanadium.  between 3.6% and 4.4% of vanadium.
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