Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
  • B22D29/001—Removing cores
  • B22D29/003—Removing cores using heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
  • B22D29/001—Removing cores
  • B22D29/002—Removing cores by leaching, washing or dissolving

Definitions

• the invention relates to the manufacture of aeronautical parts, in particular blades or rectifiers of aeronautical turbomachines, by solid-phase densification methods. More specifically, the invention relates to the counter-forms used in the manufacture of these aeronautical parts, to a method of manufacturing such a counter-form, and to a method of manufacturing such an aeronautical part.
• Metallic aeronautical parts in particular turbine blades or rectifiers, are generally made with alloys based on nickel, titanium, or titanium aluminide.
• manufacturing processes by solid phase densification can be used.
• Such manufacturing processes by solid-phase densification include, for example, sintering under load, such as flash sintering or SPS (for "Spark Plasma Sintering” in English) or hot isostatic pressing (known as H IP for " Hot Isostatic Pressing” in English), or the injection of a mixture of metal powder and a thermoplastic polymer (known as the MIM process for “Metal Injection Molding” in English).
• sintering under load such as flash sintering or SPS (for "Spark Plasma Sintering” in English) or hot isostatic pressing (known as H IP for " Hot Isostatic Pressing” in English)
• H IP Hot Isostatic Pressing
• MIM process Metal Injection Molding
• SPS sintering is a sintering method using the Joule effect to heat the pre-compacted powder, constituting the part to be manufactured (in the present application, a powder based on nickel, titanium, or aluminide of titanium) in a hollow graphite tool between two electrodes, between which a pulsed current is applied, under an inert atmosphere or under vacuum, the tool being subjected to a uniaxial pressure, for example under the action of a hydraulic press .
• the heating by Joule effect of the powder thus allows the densification of the part.
• a preform of the part to be manufactured is placed in a container evacuated to vacuum before being hermetically sealed. Homogeneous pressure in all directions is thus applied to the part, via of the container, by injecting a neutral gas under pressure (for example argon or nitrogen) into the enclosure of the container.
• a neutral gas under pressure for example argon or nitrogen
• feedstock a constituent powder of the material to be manufactured is mixed with a polymer binder.
• feedstock a constituent powder of the material to be manufactured is mixed with a polymer binder.
• feedstock a constituent powder of the material to be manufactured is mixed with a polymer binder.
• feedstock is then injected into a tool to form the part to be manufactured.
• the binder is then removed in a debinding process.
• a sintering operation on the part obtained can then be carried out.
• the graphite tooling only deforms very little during cooling, which generates differential expansions and stresses which can lead either to the breakage of tools or their premature wear, or the breakage of the densified part. This is particularly the case for the geometries of the blades with wipers and feet, or even of the straighteners.
• a method using such counter-forms conventionally comprises the manufacture of a counter-form by additive manufacturing, the partial sintering of the counter-form to give it rigidity, the filling of the counter-form with a powder to densifying, the joint SPS sintering of the constituent material of the counter-form and of the powder present inside the latter, and finally the shake-out of the counter-form to release the sintered part.
• the materials used for the counterforms are ceramics, or a composite thereof, such as yttrium oxide stabilized zirconia (YSZ), alumina reinforced zirconia (ATZ), or alumina reinforced with zirconia (ZTA).
• YSZ yttrium oxide stabilized zirconia
• ATZ alumina reinforced zirconia
• ZTA alumina reinforced with zirconia
• the titanium or titanium aluminide alloys used to manufacture the blades or the straighteners are conventionally sintered by SPS at temperatures above 1350°C.
• the above ceramic materials used for the counter-forms have a density greater than 80%, which makes their shake-out difficult and requires a specific step involving chemical or mechanical shake-out, potentially harmful for the part. subsequently manufactured and for the environment, the counter-form cannot be recycled.
• the materials used for the part to be manufactured and the counter-form have different coefficients of thermal expansion, which can cause deformation of the part in the thinnest areas such as the trailing edges, the breakage of parts, or lead to the recrystallization of certain areas under stress, inducing mechanical reductions.
• the first phase is of the "MAX phase” type, crystalline structure of generic formula M n+i AX n , combining characteristics of both metals and ceramics, and in particular having good thermal and electrical conductivity , good machinability, as well as damage tolerance and high temperature oxidation resistance.
• the use of aluminum on the A site and of carbon on the X site makes it possible to ensure good chemical compatibility with the Al 4 C 3 phase. Furthermore, the use of aluminum on site A makes it possible to ensure the formation of a protective alumina layer by oxidation of the counterform. In addition, the use of carbon on the X site is advantageous in that it does not present the risk of contaminating the materials present, nor of reacting negatively with the Al 4 C 3 phase, unlike nitrogen.
• the titanium or the chromium, used on the M site have melting temperatures higher than the temperatures used during the sintering of the part to be manufactured, making it possible to preserve their structure and their stability during the sintering.
• they have coefficients of thermal expansion compatible with those of the materials to be densified, in particular alloys based on nickel, titanium, or titanium aluminide, and good thermal conductivity.
• this first phase with a second phase of formula AI 4 C 3 is particularly advantageous.
• aluminum carbide (Al 4 C 3 ) is an inorganic compound, whose melting point is very high (2200°C), and which can easily hydrolyze at room temperature, in the presence of an atmosphere. rich in water.
• the composite material used for the counter-form of the present disclosure incorporates this second phase of aluminum carbide at the grain boundaries of the first phase. This makes it possible to make the composite material particularly reactive to atmospheres containing water.
• the degradation of the aluminum carbide is accompanied by a variation in volume and the release of gas, capable of fragmenting the grain boundary and propagating cracks in the first initial phase.
• the composite material forming the counter-form can be dense and massive initially, and be reduced to powder by hydrolysis.
• the chemical gradient between the aluminum carbide and the first phase containing aluminum and carbon is very limited, which makes it possible to limit the interdiffusion between the different chemical elements during the steps of forming the counterform and casting.
• a fragmented material composed of grains of the first phase and of hydrated aluminum can be recovered. After drying, this material can be “recharged” with AI 4 C 3 and reused to manufacture new counterforms.
• the composite material of the counter-form according to the present presentation thus combines the aforementioned advantages linked to the first phase, to the use of a second phase of formula AI 4 C 3 , allowing the production of parts of complex shapes. without having recourse to complex graphite tools, while allowing easy and rapid shake-out of the counter-form not requiring chemical solutions that are potentially harmful for the part manufactured subsequently and for the environment, and which can be recycled.
• the first phase is of one of the formulas among Cr 2 AIC, Ti 3 AIC 2 , Ti 2 AIC, Nb 4 AIC 3 , Nb 2 AIC or Mo 2 TiAIC 2 .
• the Cr 2 AIC, Ti 3 AIC 2 , Ti 2 AIC phases also have the advantage of covering the ranges of densification temperatures and thermal expansion coefficients of the materials considered and used to manufacture the part.
• the Cr 2 AIC, Ti 3 AIC 2 , Ti 2 AIC phases are aluminoforming.
• the composite material comprises between 1 and 50% of second phase by volume of the composite material, preferably between 1 and 20%. These values make it possible to ensure the fragmentation of the composite material by hydrolysis, while leaving a sufficient volume of first phase in the composite material, making it possible to retain the technical advantages associated with this first phase.
• this Al 4 C 3 phase fraction makes it possible to ensure the chemical stability of the material at high temperature, while making it possible to induce a phenomenon of hydrolysis facilitating shake-out.
• an internal surface of the counter-form is covered by a layer of alumina.
• the alumina layer has a thickness of between 1 and 50 ⁇ m. This thickness ensures the protection of the counterform during the manufacture of a part. More precisely, the alumina layer thus formed is thin enough not to have any impact on the mechanical shrinkage of the part during cooling, but chemically isolates the powder and the counter-form.
• the mixture of powders making it possible to obtain the first phase may in particular comprise the mixture of pure powders of carbon, aluminum, titanium and/or chromium, and/or chromium carbide, and/or chromium carbide, and/or titanium carbide, and/or aluminum carbide.
• the composite material constituting the counter-form is obtained by causing the various powders of the constituent elements of this material to react at high temperature.
• This method has the advantage of involving, in the production of the composite material, the Al 4 C 3 phase, making it possible to provide the necessary elements Al and C, thus providing the aforementioned advantages.
• the shaping step may comprise the injection of a binder onto a powder (called “binder jetting”), the injection of a mixture of metallic powder and of a polymer thermoplastic (or MIM process for "Metal Injection Molding” in English) or any other suitable known 3D printing process, preferably followed by sintering, or sintering under load called “flash sintering” (or SPS sintering for “Spark Plasma Sintering” in English), for example.
• the mixing step comprises mixing the pure powders constituting the first phase so as to obtain the first phase in powder form, then mixing said first phase in powder form with a Al 4 C 3 powder so as to obtain the second phase.
• the pure powders of carbon, aluminum, titanium and/or chromium and/or chromium carbide, and/or chromium carbide, and or titanium carbide, and/or aluminum carbide, for example, are mixed first, so as to obtain the first phase first, then the first phase obtained is mixed with an aluminum carbide powder in a second step, so as to obtain the second phase. This improves control of the proportions of each phase.
• the mixing step comprises mixing pure constituent powders of the first phase with an excess Al 4 C 3 powder so as to form the composite material in one operation.
• the mixing of the powders is not carried out in two stages (production of the first phase initially, then mixing with an aluminum carbide powder), but the The aforementioned pure powders are mixed in the same operation with an Al 4 C 3 powder in excess, that is to say in over-stoichiometry, thus allowing the formation of the composite material “in situ”.
• the fact of reacting the Al 4 C 3 powder in over-stoichiometry with respect to the first phase sought makes it possible to maintain a controlled volume fraction of this phase in the final material.
• a supply channel configured to allow the supply of the constituent powder of the part to be manufactured, is provided in the counter-form. shape.
• a supply channel is provided in the structure of the counter-form, so as to place the internal cavity of the counter-form forming the negative of the part to be manufactured, in fluid communication with the exterior of the counter-form.
• This channel makes it possible to facilitate the supply of powder of the constituent material of the part to be manufactured and to be densified.
• the first phase is of formula Cr 2 AIC, Ti 3 AIC 2 or Ti 2 AIC, the method comprising, after the step of shaping the counter-shape, a step of oxidation allowing the formation of an alumina layer on an internal surface of the counterform.
• the phases of formula Cr 2 AIC, Ti 3 AIC 2 or Ti 2 AIC are aluminoforming, and thus allow the formation of an alumina layer by simple oxidation of the counter-form, without requiring the addition of a complex multi-layer coating allowing the formation of this protective layer.
• This oxidation step makes it possible to produce an adherent and dense layer of alumina on a wall of the internal cavity of the counter-form forming the negative of the part to be manufactured, able to protect the composite material, to further improve the shake-out of the densified part and to limit the risks of interdiffusion between the densified powder and the composite material constituting the counterform.
• the subsequent densification step being carried out under vacuum, the latter does not pose any particular problem with respect to the composite material.
• the oxidation step is carried out by placing the counter-form in an enclosure under air between 1000 0 C and 1400 0 C.
• This presentation also relates to a method for manufacturing a metal aeronautical part, in particular a turbine part by solid-phase densification, using a counter-form obtained by a method according to any one of the preceding embodiments, the method comprising, after steps of filling the counter-form with a constituent powder of the part to be manufactured and of densifying said powder in the counter-form, a step of shake-out of the counter-form by stoving.
• the assembly is placed in a device, for example an oven, preferably with controlled humidity.
• a device for example an oven, preferably with controlled humidity.
• the presence of the Al 4 C 3 phase between the grain boundaries allows, in water-laden air, the disintegration of the core of the counterform. This facilitates the shake-out and therefore demolding of the part, while avoiding the use of chemical solutions, such as acids, potentially harmful for the manufactured part.
• the method comprises, after the shake-out step, a recovery step, in which the material shake-out by stoving is recovered so as to be reused for the manufacture of another counter-form in starting from the mixing step.
• Figure 1 shows a perspective view of a metal turbine blade comprising wipers
• FIG. 2 Figure 2 schematically represents the blade of Figure 1, and a counter-form according to the present presentation, in two parts,
• Figure 3 is a perspective view of a counter-form according to the present presentation, in one part,
• FIG. 4 Figure 4 schematically represents the steps of a method of manufacturing a metal part according to a first embodiment in accordance with the description
• Figure 5 schematically represents the steps of a method of manufacturing a metal part according to a second embodiment in accordance with the description.
• Figure 1 shows a perspective view of a turbine blade 10 comprising an airfoil 12 having an underside 13 and an upper surface 14, a blade root 15 at its lower end, and a heel 16 at its end superior.
• the blade 10 further comprises two sealing wipers 17 and 18 formed on the upper face of the heel 16 arranged transversely to the intrados 13 and extrados 14 sides.
• Such a blade is obtained, according to the present description, by densification of a powder of the constituent material of the blade, in particular alloys based on nickel (Ni), titanium (Ti), or aluminide of titanium (TiAl), in a counter-form corresponding to the negative of the part to be manufactured, that is to say of the blade 10 in the present example.
• Such a counter-form 1, in accordance with this presentation, is shown in perspective in Figure 2, with the blade 10 shown schematically in this figure.
• the counter-form 1 comprises two parts 1a and 1b arranged on either side of the blade 10, each comprising a half-cavity, and intended to be assembled to form a counter-form 1 containing a complete cavity corresponding to the negative of blade 10.
• Each half cavity respectively comprises a first portion 2a, 2b, a second portion 5a, 5b, a third portion 6a, 6b and slots 7a, 7b and 8a, 8b.
• a passage 9a, 9b is also provided in each part 1a, 1b respectively of the counter-form 1 so as to form a supply channel 9 in the counter-form 1 after assembly of the two parts 1a and 1b , and to allow the supply of the aforementioned powder constituting the blade to be manufactured, when the parts 1a and 1b are assembled.
• Figure 3 shows the against-form 1 after assembly of the two parts 1a and 1b. It will however be noted that this example is not limiting, the counter-form 1 being able to be manufactured in one piece in a single operation by a method described in more detail in the following description, so as to form a cavity comprising the different portions 2, 5, 6, 7, 8 and 9 mentioned above. [0054] Furthermore, the counter-form 1 comprises a composite material making it possible in particular to facilitate the removal of the latter, during the shake-out step described later.
• the composite material comprises two phases: a first phase called “MAX phase”, and a second phase of formula AI 4 C 3 , in other words aluminum carbide.
• the element used in group A is aluminum (Al) in order to ensure the formation of an alumina layer when aluminoforming phases are used.
• the element used at the X site is carbon (C).
• the phases containing nitrogen (N) often have lower melting temperatures than their counterparts containing carbon and the chemical compatibility with the Al 4 C 3 phase is not assured.
• the element used on site M is determined such that the melting temperature and the coefficient of thermal expansion of the MAX phases considered are compatible with the constituent materials of the part to be sintered, in particular nickel-based alloys.
• Ni having a thermal expansion coefficient of between 14 and 16x10 6 /°C
• titanium (Ti) having a thermal expansion coefficient of between 10 and 13x10 6 /°C
• titanium aluminide TiAl
• TiAl titanium aluminide
• the first phases retained can be of formula Cr 2 AIC, having a melting temperature greater than 1500° C. and a thermal expansion coefficient of approximately 13 ⁇ 10 6 /° C., TfeAIC 2 having a melting temperature above 1550°C and a coefficient of thermal expansion between 9 and 12X10 6 /°C, OR TjAlC having a melting temperature above 1550°C and a coefficient of thermal expansion between 7 and 10x10 6 /°C.
• the second phase of formula AI 4 C 3 is a known carbide whose melting temperature is very high (2200° C.). It is also aluminoforming at high temperature. Nevertheless, the particularly advantageous property in the context of the invention is the ease with which this phase exhibits hydrolysis at ambient temperature in the presence of an atmosphere rich in water.
• the decomposition of this phase follows the following reaction: AI4C3 + 1 2 H 2 0 4 AI(OH) 3 + 3 CH 4
• This reaction can be catalyzed by optimizing the level of hygrometry but also the temperature.
• the counterform 1 comprising this composite material can be easily eliminated by being degraded by hydrolysis, at the end of the blade or stator manufacturing process.
• a first example of a blade manufacturing process according to the present disclosure is a process by sintering under load, called SPS sintering (for "Spark Plasma Sintering" in English) in the following description. .
• SPS sintering for "Spark Plasma Sintering" in English
• the first step S 100 of this method consists in manufacturing the counter-form 1 described above, in one or two parts.
• step S100 for manufacturing counterform 1 is broken down into several steps. Initially, metal powders are mixed together, so as to obtain a composite powder comprising the first and the second phase (step S110).
• metal powders are mixed together, so as to obtain a composite powder comprising the first and the second phase (step S110).
• pure powders of aluminum (Al), carbon (C), chromium (Cr) and/or titanium (Ti), and/or chromium carbide (CrC), and/ or chromium carbide (Cr 7 C 3 ), and/or titanium carbide (TiC) are mixed with an excess aluminum carbide AI 4 C 3 powder, so as to form in situ a composite material comprising the first phase and the second phase, such that the second phase represents between 1 and 50%, preferably between 1 and 20% of the total volume of the composite material.
• the counter-form 1 is shaped (step S120), so that the latter takes on the desired shape.
• This step can be carried out by various known processes such as the injection of a binder onto a powder (called “binder jetting”), the injection of a mixture of metal powder and of a thermoplastic polymer (or MIM for "Metal Injection Molding” in English) or any other suitable known 3D printing process, preferably followed by sintering, or SPS sintering, for example, or any other suitable known process, or a combination of these different processes.
• a supply channel 9 is provided, allowing the subsequent injection of metal powder.
• step S130 a step of forming an alumina layer, making it possible to form a protective alumina layer with a thickness of between 1 and 50 ⁇ m can be carried out (step S130).
• This step is carried out by oxidizing the counterform 1 by bringing the latter to a temperature of between 1000 and 1400°C.
• This step is made possible by the fact that the phases of formula Cr 2 AIC, Ti 3 AIC 2 or Ti 2 AIC are aluminormous.
• the counter-form 1 thus manufactured in step S100, and comprising the cavity described above corresponding to the negative of the blade, is then filled with a constituent powder of the blade to be manufactured (step S200), in particular a powder based on titanium (Ti), a nickel-based superalloy (Ni), or an intermetallic alloy such as titanium aluminide (TiAl), via the supply channel 9.
• a constituent powder of the blade to be manufactured in particular a powder based on titanium (Ti), a nickel-based superalloy (Ni), or an intermetallic alloy such as titanium aluminide (TiAl), via the supply channel 9.
• a ultrasound table can be used to facilitate the flow of the powder in the counter-form and its filling.
• the counterform 1 containing the powder to be densified is then placed in a tool (not shown), preferably made of graphite, configured to perform the SPS sintering (step S300).
• the SPS sintering is then carried out (step S400).
• the counter-form 1 is placed in a press exerting an axial pressure on the counter-form 1.
• a pulsed current is then applied to the counter-form 1, so as to heat the powder present in it. ci by Joule effect, allowing the densification of the powder.
• the counter-form 1 is extracted from the graphite tooling, and eliminated by shake-out in order to obtain the final part (step S500).
• the step S500 of releasing the counter-form 1 can be carried out by arranging the whole in an oven with controlled hygrometry (relative humidity RH >50%) or preferably in a steam autoclave, at temperatures between 100 and 180° C., and pressures between 6 and 12 bars. The application of pressure accelerates shake-out kinetics while facilitating vapor access to thin sections.
• This step allows the disintegration of the counter-form 1, taking into account the presence of the second phase of formula AI 4 C 3 between the grain boundaries of the first phase.
• a step of cleaning and finishing the blade obtained can also be carried out.
• shake-out step S500 can be followed by a recovery step (step S600), or recycling, in which the composite material shake-out by stoving, then in powder form, is recovered so as to be reused for the manufacture of another counter-form 1, starting from the mixing step S110. More specifically, once the counter-form 1 has been degraded, a fragmented material composed of grains of the first phase and of hydrated aluminum is recovered. After drying, this material can be "reloaded” with AI 4 C 3 and reused to manufacture new counterforms 1.
• step S110 of mixing the powders is broken down into two sub-steps.
• the mixing step is carried out in a single operation, in which the composite material is formed in situ by the presence in excess of the Al 4 C 3 phase
• the step S110 of mixing the powders within the framework of the second embodiment comprises initially the mixing of pure powders making it possible to obtain the first phase (step S111), the grinding in powder form of this first phase, then the mixing the first phase thus obtained with an Al 4 C 3 powder making it possible to obtain the composite material ex situ (step S112).
• a first phase of formula Ti 3 AIC 2 can be obtained by mixing pure powders of titanium, aluminum and titanium carbide (Ti: Al: TiC ) according to the molar proportions 1: 1.05: 1.9 respectively.
• the titanium grains have a diameter of less than 45 ⁇ m, a purity of 99.5%.
• the aluminum grains have a diameter between 45 and 150 ⁇ m, a purity of 99.5% and the titanium carbide grains have a diameter of 2 ⁇ m, a purity of 99.5%, and a density of 7.82 g/cm3.
• These different powders can be mixed in a ball mixer, then subjected to reactive sintering up to 1450°C. The poous mass thus obtained is ground to be reduced to powder.
• step S600 in which the composite material decoked by stoving is recovered so as to be reused for the manufacture of another counter-form 1, the material can be "reloaded" by AI 4 C 3 starting again from step S112.
• the pure powders can also be mixed with an Al 4 C 3 powder.
• the Al 4 C 3 powder contributes to the formation of the first phase, but is not in sufficient quantity to form the composite material in situ, such that the second step S112 is necessary, and allows to add a necessary quantity of AI 4 C 3 powder, making it possible to obtain the proportions of AI 4 C 3 mentioned previously in the composite material.
• step S200 of filling the counter-form 1 with a constituent powder of the blade to be manufactured is also carried out then, in step S300, the counter-form 1 containing said powder is placed in a deformable container.
• HIP densification is performed in step S400, in which an inert gas (e.g. argon or nitrogen) is injected into the pressure vessel, then applying homogeneous pressure in all directions on the container containing the counter-form 1.
• an inert gas e.g. argon or nitrogen
• an injection of a mixture of metal powder and a thermoplastic polymer (known as the MIM process for "Metal Injection Molding" in English) can be carried out.
• the counter-form 1 is inserted into a MIM injection press and a constituent powder of the material to be manufactured, mixed with a polymer binder, is injected into the counterform 1.
• the polymer binder is then removed during a debinding process.
• a natural sintering without pressure on the part obtained can then be carried out. If the latter makes it possible to densify the part sufficiently, in particular if the relative density is greater than 99%, the shake-out of the counter-form 1, in accordance with step S500, can be carried out.
• the natural sintering can be supplemented by an SPS or HIP densification cycle under pressure, by repeating steps S300 and S400 described above.
• the debinding mentioned above can be immediately followed by SPS or HIP densification according to steps S300 and S400, without going through natural sintering.
• one or the other of the densification modes can be used for the manufacture of the metal part, and apply to both modes. embodiment described above and described with reference to Figures 4 and 5. It will be noted in particular that the steps S100 of manufacturing the counter-form 1, S500 of shake-out and S600 of recovery of the material, are common to all the densification modes ( SPS, HIP or MIM) used.

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• Manufacture Of Alloys Or Alloy Compounds (AREA)
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• 2021
  • 2021-07-16 FR FR2107728A patent/FR3125239B1/fr active Active
• 2022
  • 2022-07-08 EP EP22755244.5A patent/EP4370262A1/de active Pending
  • 2022-07-08 WO PCT/FR2022/051385 patent/WO2023285758A1/fr active Application Filing
  • 2022-07-08 CN CN202280050191.5A patent/CN117693406A/zh active Pending

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