Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/045—Alloys based on refractory metals
  • C22C1/0458—Alloys based on titanium, zirconium or hafnium
• • 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

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)

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• 2014
  • 2014-11-25 FR FR1461443A patent/FR3028784B1/fr active Active
• 2015
  • 2015-11-24 CN CN201580063833.5A patent/CN107002178B/zh active Active
  • 2015-11-24 WO PCT/FR2015/053187 patent/WO2016083724A1/fr active Application Filing
  • 2015-11-24 EP EP15817955.6A patent/EP3223981B1/de active Active
  • 2015-11-24 US US15/529,011 patent/US20170321303A1/en not_active Abandoned

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