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EP3325681A1 - Process for manufacturing an al/al3b48c3 composite - Google Patents

Process for manufacturing an al/al3b48c3 composite

Info

Publication number
EP3325681A1
EP3325681A1 EP16741604.9A EP16741604A EP3325681A1 EP 3325681 A1 EP3325681 A1 EP 3325681A1 EP 16741604 A EP16741604 A EP 16741604A EP 3325681 A1 EP3325681 A1 EP 3325681A1
Authority
EP
European Patent Office
Prior art keywords
crucible
powder
graphite
composite material
temperature
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
EP16741604.9A
Other languages
German (de)
French (fr)
Other versions
EP3325681B1 (en
Inventor
Olivier DEZELLUS
Laurent CHAFFRON
Jérôme ANDRIEUX
Nassim SAMER
Bruno GARDIOLA
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.)
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date 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 date listed.)
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Publication of EP3325681A1 publication Critical patent/EP3325681A1/en
Application granted granted Critical
Publication of EP3325681B1 publication Critical patent/EP3325681B1/en
Not-in-force 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/062—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on B4C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • C22C32/0057—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on B4C

Definitions

  • the present invention relates to the field of synthesis of metal matrix composite materials and ceramic particulate reinforcements.
  • the invention relates to a method for preparing a composite material having an aluminum matrix having dispersed therein reinforcements Al3B 4 8C 2.
  • This process can notably be applied in the fields of aeronautics and the automobile.
  • CMM metal matrix materials
  • metal matrix materials which comprise a metal matrix (metal or metal alloy) in which are incorporated reinforcements (particles, fibers or other) metal or ceramic
  • CMM metal matrix materials
  • the advantage of CMM compared to light alloys (based on aluminum, magnesium or titanium) is that they have ratios E / p (elastic modulus / density) and ⁇ / ⁇ (limit of elasticity / density) very high.
  • the composite material AI / B 4 C which is a particularly useful composite material that boron carbide is one of the most known hard material, it is lightweight and has a higher melting temperature at 2400 ° C.
  • the chemical reactivity must also be controlled. Indeed, the equilibrium between the phases in the Al-BC system indicates that Al and B 4 C are not in equilibrium below a temperature which is not precisely known, but which is estimated in the literature to be superior at 1400 ° C.
  • any synthesis based on the mixture of precursor powders of Al and B 4 C and carried out at a temperature below 1400 ° C therefore leads to the decomposition of the reinforcement B 4 C by Al and the formation of carbide AI3BC3.
  • the latter although less sensitive to hydrolysis in the presence of moisture than the carbide AI 4 C3, still remains subject to this phenomenon which leads to the release of large amounts of CH 4 gas.
  • the gas produced at the core of the composite material then generates stresses that lead to the ruin of the composite material (return to the powder state).
  • other phases such as borides AIB 2 and AIB12 can also be formed during the interaction between Al and B 4 C. The fragility of these phases then induces embrittlement of the composite material.
  • the first solution which will be called the cryogenic method, was developed by Julie Schoenung at the University of California, Davis. This method encounters the difficulty of implementing high energy grinding in liquid nitrogen for large quantities of material. The change of scale from laboratory to industrial production seems difficult. Moreover, this method can not ignore a consolidation step that must be carried out hot.
  • the second solution is to minimize the duration of the hot consolidation step to limit as far as possible the progress of the reaction between Al and B 4 C.
  • the main difficulty lies again in the amount of usable material. Indeed, the hot forming requires that the matrix Al is brought to a temperature sufficient to be subject to plastic deformation by creep. However, in the case of a large volume of material, the standardization of the temperature da ns the entire volume requires a significant temperature maintenance time also.
  • the inventors have therefore set themselves the goal of designing a process for producing an alternative composite material to the composite AI / B 4 C, which has properties similar to those of the composite AI / B 4 C, while being able to be produced industrially. .
  • the graphite element for closing the cavity is a graphite piston.
  • the AIB 2 powder When placed in the graphite crucible in step a), the AIB 2 powder may be in various forms. According to a first variant, the powder is placed in the crucible in a compressed form, for example in the form of one or more pellets. According to a second variant, the powder is placed in the crucible in a powder form and step b) further comprises a compression of the powder. It is preferred to use the powder in powder form and compress it in the cavity of the crucible, since the AIB 2 diborure is weakly ductile, obtaining a compact is difficult.
  • step b) when the powder is placed in the crucible in pulverulent form, step b) further comprises the compression of the powder.
  • the compression of the powder and the closing of the cavity of the crucible are obtained by the use of a graphite piston.
  • the piston is dimensioned so as to slide in the opening of the crucible in order to compress the powder and to close this opening.
  • the crucible is heated at a temperature ranging from 1000 ° C. to 1400 ° C. for a period ranging from 5 minutes to 30 minutes.
  • the descent in temperature in step d) is fast. This makes it possible to limit the decomposition reactions of the phases formed at high temperature.
  • the cooling in step d) comprises a descent in temperature with a speed greater than or equal to 10 ° C / s until reaching 600 ° C.
  • step e) The elimination of the crucible in step e) can be obtained separating the ingot of composite material obtained at the end of step d) (and which forms the composite material part to obtain) crucible or by proceeding to a turning operation that will destroy the crucible.
  • the composite material AI / Al3B 4 8C 2 is made according the method of the invention is a good alternative to the composite material AI / B 4 C.
  • the ternary compound T3-Al3B 4 SC 2 which form the reinforcement is in equilibrium with the Al matrix according to the literature.
  • it has properties similar to those of B 4 C, as can be seen from the table below, and is therefore a credible alternative to B 4 C for the production of a ceramic matrix composite and reinforcement of carbide type rich in boron.
  • the matrix and the reinforcement are formed at high temperature and in-situ, which has several advantages.
  • the reinforcements of the composite are obtained during the decomposition of the AIB 2 particles by germination / growth in the liquid phase.
  • the matrix / reinforcement interface is therefore chemically clean (no impurities, oxides or other) and thus leads to optimum resistance of the interface.
  • the reinforcements are formed in situ and have not had to undergo a grinding cycle, grinding which is often likely to induce defects which are then starting points for the cracking of the composite material.
  • the method which is the subject of the invention also has the advantage of the simplicity of its implementation.
  • it makes it possible to obtain a dense ingot directly from the internal geometry of the graphite crucible, since the ingot is shaped in the liquid state in the graphite crucible.
  • the single figure is an image obtained by scanning electron microscopy of an ingot obtained according to a first embodiment according to the method which is the subject of the invention.
  • the method which is the subject of the invention is based on a so-called reactive synthesis method.
  • the matrix and the reinforcement of the composite material are obtained in situ by a reaction between two precursors.
  • the precursors chosen are aluminum diboride (AIB 2 ) and graphite (C).
  • AIB 2 is in the form of a powder and is placed in a crucible which is made of graphite.
  • the same graphite element preferably a graphite piston, is used to compact the powder and to seal the cavity of the crucible.
  • the whole is then heated to high temperature.
  • the heating is performed at a temperature above the decomposition temperature of AIB 2 , that is to say the temperature from which one begins to have a liquid phase.
  • the decomposition temperature of AIB 2 i.e. at 960 ° C, two phases are obtained, a liquid phase and a solid phase.
  • the heating is carried out at a temperature of between 1000 ° C. and 1400 ° C., preferably between 1200 ° C. and 1400 ° C., for a period of time. which can be variable, but will generally be between 5 and 30 minutes. In fact, the duration of heating at a given temperature is adjusted according to the desired microstructure: the longer the heating time, the larger the size of the reinforcing particles.
  • the two phases AIB 2 and C is not in equilibrium, they react together to form the mixed carbide and Al Al3B 4 8C 2.
  • the climbs and descents in temperature are fast, in order to limit both the size of the reinforcing particles and their decomposition during cooling.
  • the graphite crucible can be removed by simple machining, releasing the ingot of CMM composite material contained therein. Since this was obtained at a temperature higher than the Al fusion, the presence of the matrix in the liquid state makes it possible to directly obtain a composite with a relative density greater than 99.5%.
  • the microstructure of the AI / Al3B 4 sC 2 composite thus obtained is observed under SEM (single figure).
  • the white phase corresponds to the aluminum matrix and the black particles correspond to the reinforcement phase Al3B 4 sC 2 . It is found that the reinforcements are homogeneously dispersed in the matrix and have a size of between 200 nm and 5 ⁇ (average size of about 700 nm).
  • the method of the invention makes it possible to create an interface between a matrix and a reinforcement which is mechanically strong, but without leading to the decomposition of the reinforcement and the creation of deleterious secondary phases for the properties of the composite. Indeed, during the reactive synthesis between AIB 2 and graphite (C), there are very few minor phases are formed and the composite thus essentially comprises a phase of Al (the matrix) and a phase of Al3B 4 8C 2 (reinforcement), the minor phases being present in minimal amounts.
  • the process according to the invention provides a new synthetic route for producing, in a simple manner and in quantity, Al-matrix composite materials reinforced with particles of a mixed boron (B) and aluminum (Al) carbide. whose properties are close to those of a B 4 C reinforcement.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

The invention relates to a process for manufacturing a part made of an Al/Al3B48C2 composite material comprising an aluminium matrix in which particles of a mixed carbide of chemical formula Al3B48C2 are dispersed. The process comprises the following steps: a) placing a powder of chemical formula AlB2 in the cavity of a graphite crucible; b) closing the cavity with a graphite element; c) heating the crucible at a temperature at least equal to 960°C and less than or equal to 1400°C in order to obtain the formation of precipitates of the mixed carbide of chemical formula Al3B48C2 in liquid aluminium; d) cooling the crucible in order to solidify the liquid aluminium; e) removal from the crucible; by which means the part made of Al/Al3B48C2 composite material is obtained.

Description

PROCEDE DE FABRICATION D'UNE PIECE  METHOD FOR MANUFACTURING A PIECE
EN UN MATERIAU COMPOSITE AI/AI3B48C2 IN A COMPOSITE MATERIAL AI / AI 3 B 48 C 2
DESCRIPTIONDESCRIPTION
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention se rapporte au domaine de la synthèse de matériaux composites à matrice métallique et à renforts particulaires céramiques. The present invention relates to the field of synthesis of metal matrix composite materials and ceramic particulate reinforcements.
En particulier, l'invention concerne un procédé d'élaboration d'un matériau composite ayant une matrice en aluminium dans laquelle sont dispersés des renforts en Al3B48C2. In particular, the invention relates to a method for preparing a composite material having an aluminum matrix having dispersed therein reinforcements Al3B 4 8C 2.
Ce procédé peut notamment trouver application dans les domaines de l'aéronautique et de l'automobile.  This process can notably be applied in the fields of aeronautics and the automobile.
ÉTAT DE LA TECHNIQUE ANTÉRIEURE STATE OF THE PRIOR ART
Dans le domaine de l'automobile et de l'aéronautique, les industriels cherchent à obtenir des matériaux légers et résistants. Or, la plupart des matériaux industrialisables légers sont très peu résistants. In the automotive and aerospace industries, manufacturers are seeking lightweight and durable materials. However, most light industrializable materials are very weak.
C'est la raison pour laquelle les matériaux à matrice métallique (CMM), qui comprennent une matrice métallique (métal ou alliage métallique) dans laquelle sont incorporés des renforts (particules, fibres ou autres) métalliques ou céramiques, sont particulièrement appréciés. En effet, l'intérêt des CMM par rapport aux alliages légers (à base d'aluminium, de magnésium ou de titane) est qu'ils présentent des rapports E/p (module élastique/masse volumique) et σ/ρ (limite d'élasticité/masse volumique) très élevés.  This is the reason why metal matrix materials (CMM), which comprise a metal matrix (metal or metal alloy) in which are incorporated reinforcements (particles, fibers or other) metal or ceramic, are particularly preferred. Indeed, the advantage of CMM compared to light alloys (based on aluminum, magnesium or titanium) is that they have ratios E / p (elastic modulus / density) and σ / ρ (limit of elasticity / density) very high.
Un des principaux problèmes à résoudre lors de l'élaboration d'un matériau à matrice métallique est celui de la réactivité chimique entre la matrice et le renfort. Cette réactivité est en effet nécessaire pour que l'interface entre la matrice et le renfort soit mécaniquement résistante, mais elle peut également conduire à des effets secondaires catastrophiques pour le matériau composite. Cette réactivité doit donc être rigoureusement contrôlée. One of the main problems to solve in the development of a metal matrix material is that of the chemical reactivity between the matrix and the reinforcement. This reactivity is indeed necessary so that the interface between the matrix and the reinforcement is mechanically resistant, but it can also lead to effects. catastrophic side effects for the composite material. This reactivity must therefore be strictly controlled.
Prenons l'exemple du matériau composite AI/B4C, qui est un matériau composite particulièrement intéressant du fait que le carbure de bore est l'un des matériaux les plus durs connus, qu'il est léger et a une température de fusion supérieure à 2400°C. For example, the composite material AI / B 4 C, which is a particularly useful composite material that boron carbide is one of the most known hard material, it is lightweight and has a higher melting temperature at 2400 ° C.
La réactivité chimique entre la phase Al et la phase B4C du composite AI/B4C est nécessaire, car l'aluminium liquide ne mouille pas les particules de B4C, ce qui implique une difficulté à assurer au sein du matériau composite une interface intime entre les deux phases. En conséquence, le travail d'adhésion, à savoir la force chimique de l'interface, sera faible au sein du matériau composite, ce qui conduit à une interface mécaniquement faible. Or, dans la plupart des composites à matrice métallique et renfort céramique, il y a un objectif de transfert de la charge mécanique depuis la matrice vers le renfort au travers de l'interface : celle-ci doit donc être mécaniquement résistante. The chemical reactivity between the Al phase and the B 4 C phase of the AI / B 4 C composite is necessary because the liquid aluminum does not wet the B 4 C particles, which implies a difficulty in ensuring within the composite material an intimate interface between the two phases. As a result, the adhesion work, ie the chemical force of the interface, will be weak within the composite material, leading to a mechanically weak interface. However, in most metal matrix composites and ceramic reinforcement, there is an objective of transfer of the mechanical load from the matrix to the reinforcement through the interface: it must therefore be mechanically resistant.
Cependant, la réactivité chimique doit également être maîtrisée. En effet, les équilibres entre les phases dans le système Al-B-C indiquent que Al et B4C ne sont pas en équilibre en dessous d'une température qui n'est pas précisément connue, mais qui est estimée dans la littérature comme étant supérieure à 1400°C. However, the chemical reactivity must also be controlled. Indeed, the equilibrium between the phases in the Al-BC system indicates that Al and B 4 C are not in equilibrium below a temperature which is not precisely known, but which is estimated in the literature to be superior at 1400 ° C.
Ainsi, toute synthèse reposant sur le mélange de poudres de précurseurs de Al et B4C et effectuée à une température inférieure à 1400°C conduit donc à la décomposition du renfort B4C par Al et à la formation du carbure AI3BC3. Ce dernier, bien que moins sensible à l'hydrolyse en présence d'humidité que le carbure AI4C3, reste tout de même sujet à ce phénomène qui conduit à la libération de grandes quantités de CH4 gazeux. Le gaz produit au cœur du matériau composite génère alors des contraintes qui conduisent à la ruine du matériau composite (retour à l'état de poudre). Par ailleurs, d'autres phases comme les borures AIB2 et AIB12 peuvent également être formées lors de l'interaction entre Al et B4C. La fragilité de ces phases induit alors une fragilisation du matériau composite. Thus, any synthesis based on the mixture of precursor powders of Al and B 4 C and carried out at a temperature below 1400 ° C therefore leads to the decomposition of the reinforcement B 4 C by Al and the formation of carbide AI3BC3. The latter, although less sensitive to hydrolysis in the presence of moisture than the carbide AI 4 C3, still remains subject to this phenomenon which leads to the release of large amounts of CH 4 gas. The gas produced at the core of the composite material then generates stresses that lead to the ruin of the composite material (return to the powder state). Moreover, other phases such as borides AIB 2 and AIB12 can also be formed during the interaction between Al and B 4 C. The fragility of these phases then induces embrittlement of the composite material.
Une synthèse effectuée à haute température (au moins supérieure à 1400°C) dans le domaine où Al et B4C sont en équilibre serait quant à elle confrontée à la même difficulté, mais cette fois a u cours du refroidissement conduisant alors aux mêmes conséquences. A synthesis carried out at high temperature (at least greater than 1400 ° C) in the area where Al and B 4 C are in equilibrium would be confronted with the same difficulty, but this time during the cooling then leading to the same consequences.
Les solutions envisagées dans la littérature pour réaliser un composite AI/B4C visent à résoudre le problème de réactivité en agissant sur la cinétique de réaction, soit en se plaçant à très basse température (cryogénique) dans l'objectif de ralentir au maximum la cinétique de réaction entre Al et B4C, soit en limitant le temps d'interaction à haute température lors de l'étape de consolidation/mise en forme. Mais ces solutions ne sont pas adaptées à une production industrielle. The solutions envisaged in the literature to produce a composite AI / B 4 C aim to solve the problem of reactivity by acting on the kinetics of reaction, either by placing at very low temperature (cryogenic) in order to slow down as much as possible. kinetics of reaction between Al and B 4 C, or by limiting the time of high temperature interaction during the step of consolidation / shaping. But these solutions are not suitable for industrial production.
La première solution, que l'on appellera « méthode cryogénique », a été développée par Julie Schoenung à l'Université de Californie à Davis. Cette méthode se heurte à la difficulté de mettre en œuvre un broyage haute énergie dans de l'azote liquide pour de grandes quantités de matière. Le changement d'échelle du laboratoire à la production industrielle parait difficile. Par ailleurs, cette méthode ne peut pas faire l'impasse sur une étape de consolidation qui doit être réalisée à chaud.  The first solution, which will be called the cryogenic method, was developed by Julie Schoenung at the University of California, Davis. This method encounters the difficulty of implementing high energy grinding in liquid nitrogen for large quantities of material. The change of scale from laboratory to industrial production seems difficult. Moreover, this method can not ignore a consolidation step that must be carried out hot.
La seconde solution consiste à minimiser la durée de l'étape de consolidation à chaud afin de limiter autant que possible l'avancement de la réaction entre Al et B4C. La principale difficulté réside là encore dans la quantité de matière utilisable. En effet, la mise en forme à chaud nécessite que la matrice Al soit portée à une température suffisante pour être sujette à la déformation plastique par fluage. Or, dans le cas d'un volume de matière important, l'uniformisation de la température da ns l'ensemble du volume nécessite un temps de maintien en température important également. The second solution is to minimize the duration of the hot consolidation step to limit as far as possible the progress of the reaction between Al and B 4 C. The main difficulty lies again in the amount of usable material. Indeed, the hot forming requires that the matrix Al is brought to a temperature sufficient to be subject to plastic deformation by creep. However, in the case of a large volume of material, the standardization of the temperature da ns the entire volume requires a significant temperature maintenance time also.
Une troisième solution combinant ces deux approches a été proposée par l'équipe de Julie Schoenung et a fait l'objet d'une demande de brevet (document [1]). Elle consiste à mélanger et à broyer des poudres de précurseurs de Al et B4C dans de l'azote liquide (cryobroyage), à compacter à froid le mélange, puis à fritter le mélange compacté par la technique SPS (pour « Spark Plasma Sintering » en anglais), dite de frittage flash, qui permet de porter le mélange compacté à haute température penda nt un temps plus court que par les techniques de chauffe classiques. Cette troisième solution ne résout cependant pas le problème du changement d'échelle pour l'étape de cryobroyage. A third solution combining these two approaches was proposed by Julie Schoenung's team and was the subject of a patent application (document [1]). It consists of mixing and grinding Al and B 4 C precursor powders in liquid nitrogen (freeze-grinding), cold-compacting the mixture and then sintering the compacted mixture by the SPS technique (for "Spark Plasma Sintering"). In English), known as flash sintering, which makes it possible to wear the compacted mixture at high temperature for a shorter time than by conventional heating techniques. This third However, this solution does not solve the problem of scaling for the cryomilling step.
Ainsi, du fait de la réactivité entre Al et B4C, les méthodes classiques consistant à mélanger, compacter et densifier les poudres ne sont pas satisfaisantes, sauf à les mettre en œuvre dans le cadre de techniques cryogéniques. Cependant, de telles techniques cryogéniques sont lourdes à mettre en œuvre, coûteuses et ne sont pas adaptés à une production de volume de matière important. Thus, because of the reactivity between Al and B 4 C, the conventional methods of mixing, compacting and densifying the powders are not satisfactory, except to implement them in the context of cryogenic techniques. However, such cryogenic techniques are cumbersome to implement, expensive and are not suitable for large volume production of material.
Les Inventeurs se sont donc fixé comme but de concevoir un procédé d'élaboration d'un matériau composite alternatif au composite AI/B4C, qui ait des propriétés proches de celles du composite AI/B4C, tout en pouvant être réalisé industriellement. The inventors have therefore set themselves the goal of designing a process for producing an alternative composite material to the composite AI / B 4 C, which has properties similar to those of the composite AI / B 4 C, while being able to be produced industrially. .
EXPOSÉ DE L'INVENTION STATEMENT OF THE INVENTION
Ce but est atteint grâce à un procédé de fabrication d'une pièce en un matériau composite AI/Al3B4sC2 comprenant une matrice en aluminium dans laquelle sont dispersées des particules d'un carbure mixte de formule chimique Al3B48C2, ledit procédé comprenant les étapes suivantes : This object is achieved by a method of manufacturing a piece of composite material AI / Al3B 4 sC 2 comprising an aluminum matrix having dispersed therein particles of a mixed carbide of chemical formula 4 Al3B 8C 2, said method comprising the following steps:
a) la mise en place d'une poudre de formule chimique AIB2 dans la cavité d'un creuset en graphite ; a) the establishment of a powder of chemical formula AIB 2 in the cavity of a graphite crucible;
b) la fermeture de la cavité par un élément en graphite ; c) le chauffage du creuset à une température au moins égale à 960°C et inférieure ou égale à 1400°C pour obtenir la formation de précipités du carbure mixte de formule chimique Al3B4gC2 dans de l'aluminium liquide ; b) closing the cavity by a graphite element; c) heating the crucible at a temperature of at least 960 ° C and less than or equal to 1400 ° C to obtain the formation of precipitates of the mixed carbide of chemical formula Al3B 4 gC 2 in liquid aluminum;
d) le refroidissement du creuset pour solidifier l'aluminium liquide ; e) l'élimination du creuset ;  d) cooling the crucible to solidify the liquid aluminum; e) elimination of the crucible;
moyennant quoi on obtient la pièce en matériau composite AI/Al3B4sC2.whereby the composite material part AI / Al3B 4 sC 2 is obtained.
De préférence, l'élément en graphite servant à fermer la cavité est un piston en graphite. Preferably, the graphite element for closing the cavity is a graphite piston.
Lorsqu'elle est mise en place dans le creuset en graphite à l'étape a), la poudre de AIB2 peut être sous différentes formes. Selon une première variante, la poudre est mise en place dans le creuset sous une forme compressée, par exemple sous la forme d'une ou plusieurs pastilles. Selon une deuxième variante, la poudre est mise en place dans le creuset sous une forme pulvérulente et l'étape b) comprend de plus une compression de la poudre. On préfère utiliser la poudre sous forme pulvérulente et la compresser dans la cavité du creuset, car le diborure AIB2 étant faiblement ductile, l'obtention d'un compact est difficile. When placed in the graphite crucible in step a), the AIB 2 powder may be in various forms. According to a first variant, the powder is placed in the crucible in a compressed form, for example in the form of one or more pellets. According to a second variant, the powder is placed in the crucible in a powder form and step b) further comprises a compression of the powder. It is preferred to use the powder in powder form and compress it in the cavity of the crucible, since the AIB 2 diborure is weakly ductile, obtaining a compact is difficult.
Selon une variante préférée de l'invention, lorsque la poudre est mise en place dans le creuset sous forme pulvérulente, l'étape b) comprend en outre la compression de la poudre. De préférence, la compression de la poudre et la fermeture de la cavité du creuset sont obtenus par l'utilisation d'un piston en graphite. Le piston est dimensionné de manière à pouvoir coulisser dans l'ouverture du creuset afin de compresser la poudre et d'obturer cette ouverture.  According to a preferred variant of the invention, when the powder is placed in the crucible in pulverulent form, step b) further comprises the compression of the powder. Preferably, the compression of the powder and the closing of the cavity of the crucible are obtained by the use of a graphite piston. The piston is dimensioned so as to slide in the opening of the crucible in order to compress the powder and to close this opening.
De préférence, à l'étape c), le creuset est chauffé à une température allant de 1000°C à 1400°C pendant une durée allant de 5 minutes à 30 minutes.  Preferably, in step c), the crucible is heated at a temperature ranging from 1000 ° C. to 1400 ° C. for a period ranging from 5 minutes to 30 minutes.
De préférence, la descente en température à l'étape d) est rapide. Cela permet de limiter les réactions de décomposition des phases formées à haute température. Préférentiellement, le refroidissement à l'étape d) comprend une descente en température avec une vitesse supérieure ou égale à 10°C/s jusqu'à atteindre 600°C.  Preferably, the descent in temperature in step d) is fast. This makes it possible to limit the decomposition reactions of the phases formed at high temperature. Preferably, the cooling in step d) comprises a descent in temperature with a speed greater than or equal to 10 ° C / s until reaching 600 ° C.
L'élimination du creuset à l'étape e) peut être obtenue séparant le lingot en matériau composite obtenu à l'issue de l'étape d) (et qui forme la pièce en matériau composite à obtenir) du creuset ou bien encore en procédant à une opération de tournage qui va détruire le creuset.  The elimination of the crucible in step e) can be obtained separating the ingot of composite material obtained at the end of step d) (and which forms the composite material part to obtain) crucible or by proceeding to a turning operation that will destroy the crucible.
Le matériau composite AI/Al3B48C2 réalisé selon le procédé objet de l'invention est une bonne alternative au matériau composite AI/B4C. En effet, le composé ternaire T3-Al3B4sC2, qui forme le renfort, est en équilibre avec la matrice Al selon la littérature. En outre, il possède des propriétés similaires à celles de B4C, comme on peut le constater en consultant le tableau ci-dessous, et constitue donc une alternative crédible à B4C pour la production d'un composite à matrice céramique et renfort de type carbure riche en bore. Composé Densité Module Knoop Vickers Ténacité Conductivité (g. cm 3) (GPa) (GPa) (GPa) (MPa.m1/2) thermique The composite material AI / Al3B 4 8C 2 is made according the method of the invention is a good alternative to the composite material AI / B 4 C. In fact, the ternary compound T3-Al3B 4 SC 2, which form the reinforcement is in equilibrium with the Al matrix according to the literature. In addition, it has properties similar to those of B 4 C, as can be seen from the table below, and is therefore a credible alternative to B 4 C for the production of a ceramic matrix composite and reinforcement of carbide type rich in boron. Compound Density Module Knoop Vickers Toughness Conductivity (gcm 3 ) (GPa) (GPa) (GPa) (MPa.m 1/2 ) thermal
(W.m^.K 1) (Wm ^ .K 1 )
Al3B4sC2 2,62 - 23 - 37 25 - 30 4 - 5,3 19,6 (310K) Al3B 4 sC 2 2.62 - 23 - 37 25 - 30 4 - 5.3 19.6 (310K)
B4C 2,52 450 - 470 39 - 37 38 3 - 4 30 - 42 B 4 C 2.52 450 - 470 39 - 37 38 3 - 4 30 - 42
Selon le procédé objet de l'invention, la matrice et le renfort (et par conséquent l'interface) sont formés à haute température et in-situ, ce qui présente plusieurs avantages. According to the method of the invention, the matrix and the reinforcement (and therefore the interface) are formed at high temperature and in-situ, which has several advantages.
Tout d'abord, cela permet de s'affranchir de la difficulté liée à l'élimination des films d'oxydes présents sur les particules d'AIB2. La réactivité entre AIB2 et le carbone du creuset en graphite élimine cette barrière d'oxyde qui limite le mouillage, l'adhésion et la résistance mécanique de l'interface. First of all, this makes it possible to overcome the difficulty associated with the removal of the oxide films present on the AIB 2 particles. The reactivity between AIB 2 and the graphite crucible carbon eliminates this oxide barrier which limits the wetting, adhesion and mechanical strength of the interface.
Les renforts du composite sont obtenus lors de la décomposition des particules d'AIB2 par germination/croissance dans la phase liquide. L'interface matrice/renfort est donc chimiquement propre (pas d'impuretés, oxydes ou autres) et conduit donc à une résistance optimale de l'interface. The reinforcements of the composite are obtained during the decomposition of the AIB 2 particles by germination / growth in the liquid phase. The matrix / reinforcement interface is therefore chemically clean (no impurities, oxides or other) and thus leads to optimum resistance of the interface.
Les renforts sont formés in situ et n'ont pas eu à subir un cycle de broyage, broyage qui est souvent susceptible d'induire des défauts qui sont ensuite des points d'amorce pour la fissuration du matériau composite.  The reinforcements are formed in situ and have not had to undergo a grinding cycle, grinding which is often likely to induce defects which are then starting points for the cracking of the composite material.
Par ailleurs, le procédé objet de l'invention présente également l'avantage de la simplicité de sa mise en œuvre. Il permet notamment d'obtenir directement un lingot dense à la géométrie interne du creuset en graphite, puisque la mise en forme du lingot se fait à l'état liquide dans le creuset en graphite.  Moreover, the method which is the subject of the invention also has the advantage of the simplicity of its implementation. In particular, it makes it possible to obtain a dense ingot directly from the internal geometry of the graphite crucible, since the ingot is shaped in the liquid state in the graphite crucible.
Les applications potentielles du procédé objet de l'invention sont nombreuses. On peut notamment citer les domaines nécessitant la production de pièces allégées (pièces pour l'aéronautique (avion, hélicoptère, etc.), pour l'automobile, etc.). On peut également citer les domaines qui nécessitent la production de pièces à forte conductivité thermique par la présence de la matrice en aluminium, mais à faible coefficient de dilatation thermique par la présence d'un taux de particules de renforts élevé. De telles pièces permettent d'évacuer la chaleur et possèdent une bonne stabilité dimensionnelle et sont donc susceptibles d'intérêt pour des applications dans le secteur spatial ou encore en électronique de puissance. Enfin, la production de pièces légères comprenant un fort taux d'un renfort céramique présentant une dureté élevée peut également trouver une application da ns le secteur balistique à des fins de protection des personnes. The potential applications of the method which is the subject of the invention are numerous. These include areas requiring the production of lighter parts (parts for aeronautics (aircraft, helicopter, etc.), for the automobile, etc.). We can also mention the areas that require the production of parts with high thermal conductivity by the presence of the aluminum matrix, but low coefficient of thermal expansion by the presence of a rate of particles of reinforcements Student. Such parts can evacuate heat and have good dimensional stability and are therefore of interest for applications in the space sector or in power electronics. Finally, the production of lightweight parts comprising a high rate of a ceramic reinforcement having a high hardness can also find application in the ballistic sector for personal protection purposes.
D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture du complément de description qui suit et qui se réfère à la figure annexée.  Other features and advantages of the invention will appear better on reading the additional description which follows and which refers to the appended figure.
Bien entendu, ce complément de description n'est donné qu'à titre d'illustration de l'invention et ne constitue en aucun cas une limitation de celle-ci.  Of course, this additional description is given by way of illustration of the invention and does not constitute in any way a limitation thereof.
BRÈVE DESCRIPTION DE LA FIGURE UNIQUE BRIEF DESCRIPTION OF THE SINGLE FIGURE
La figure unique est une image obtenue par microscopie électronique à balayage d'un lingot obtenu selon un premier mode de réa lisation selon le procédé objet de l'invention. EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERS The single figure is an image obtained by scanning electron microscopy of an ingot obtained according to a first embodiment according to the method which is the subject of the invention. DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
Le procédé objet de l'invention repose sur une méthode de synthèse dite réactive. En effet, la matrice et le renfort du matériau composite sont obtenus in situ par une réaction entre deux précurseurs. Les précurseurs choisis sont le diborure d'aluminium (AIB2) et le graphite (C). AIB2 est sous la forme d'une poudre et est placé dans un creuset qui est en graphite. De préférence, un même élément en graphite, de préférence un piston en graphite, est utilisé pour compacter la poudre et pour fermer hermétiquement la cavité du creuset. L'ensemble est ensuite porté à haute température. Le chauffage est réalisé à une température supérieure à la température de décomposition d'AIB2, c'est-à-dire la température à partir de laquelle on commence à avoir une phase liquide. En fait, à la température de décomposition d'AIB2, c'est-à-dire à 960°C, on obtient deux phases, une phase liquide et une phase solide. The method which is the subject of the invention is based on a so-called reactive synthesis method. Indeed, the matrix and the reinforcement of the composite material are obtained in situ by a reaction between two precursors. The precursors chosen are aluminum diboride (AIB 2 ) and graphite (C). AIB 2 is in the form of a powder and is placed in a crucible which is made of graphite. Preferably, the same graphite element, preferably a graphite piston, is used to compact the powder and to seal the cavity of the crucible. The whole is then heated to high temperature. The heating is performed at a temperature above the decomposition temperature of AIB 2 , that is to say the temperature from which one begins to have a liquid phase. In fact, at the decomposition temperature of AIB 2 , i.e. at 960 ° C, two phases are obtained, a liquid phase and a solid phase.
De préférence, le chauffage est réalisé à une température comprise entre 1000°C et 1400°C, préférentiellement entre 1200°C et 1400°C, pendant une durée qui peut être variable, mais qui sera généralement comprise entre 5 et 30 minutes. En fait, la durée du chauffage à une température donnée est ajustée en fonction de la microstructure que l'on souhaite obtenir : plus la durée du chauffage est longue, plus la taille des particules de renfort sera importante. Preferably, the heating is carried out at a temperature of between 1000 ° C. and 1400 ° C., preferably between 1200 ° C. and 1400 ° C., for a period of time. which can be variable, but will generally be between 5 and 30 minutes. In fact, the duration of heating at a given temperature is adjusted according to the desired microstructure: the longer the heating time, the larger the size of the reinforcing particles.
Les deux phases AIB2 et C n'étant pas en équilibre, elles réagissent entre elles pour former Al et le carbure mixte Al3B48C2. The two phases AIB 2 and C is not in equilibrium, they react together to form the mixed carbide and Al Al3B 4 8C 2.
De préférence, les montées et les descentes en température sont rapides, dans l'objectif de limiter à la fois la taille des particules de renfort et leur décomposition lors du refroidissement.  Preferably, the climbs and descents in temperature are fast, in order to limit both the size of the reinforcing particles and their decomposition during cooling.
A l'issue de la synthèse à haute température, le creuset graphite peut être éliminé par un simple usinage, libérant alors le lingot de matériau composite CMM contenu à l'intérieur. Celui-ci ayant été obtenu à une température supérieure à la fusion de Al, la présence de la matrice à l'état liquide permet d'obtenir directement un composite avec une densité relative supérieure à 99,5%.  At the end of the high temperature synthesis, the graphite crucible can be removed by simple machining, releasing the ingot of CMM composite material contained therein. Since this was obtained at a temperature higher than the Al fusion, the presence of the matrix in the liquid state makes it possible to directly obtain a composite with a relative density greater than 99.5%.
Nous allons à présent réaliser un matériau composite AI/Al3B4sC2 selon le procédé objet de l'invention. We will now make a composite material AI / Al3B 4 sC 2 according to the method object of the invention.
Dans un creuset en graphite de 8 mm de diamètre, d'une hauteur de 5 mm et dont les parois ont une épaisseur de 2 mm, on place 750 mg de poudre de diborure d'aluminium (AIB2). L'ensemble est chauffé à 1400°C pendant 15 minutes. La rampe de chauffe est d'environ 340°C/min., tandis que le refroidissement est obtenu en trempant le creuset directement dans un bain d'huile refroidi à 0°C. In a graphite crucible 8 mm in diameter, with a height of 5 mm and whose walls have a thickness of 2 mm, 750 mg of aluminum diboride powder (AIB 2 ) are placed. The whole is heated at 1400 ° C for 15 minutes. The heating ramp is about 340 ° C / min, while cooling is obtained by dipping the crucible directly in an oil bath cooled to 0 ° C.
La microstructure du composite AI/Al3B4sC2 ainsi obtenu est observée sous MEB (figure unique). La phase blanche correspond à la matrice aluminium et les particules noires correspondent à la phase de renfort Al3B4sC2. On constate que les renforts sont dispersés dans la matrice de manière homogène et ont une taille comprise entre 200 nm et 5 μιη (taille moyenne d'environ 700 nm). The microstructure of the AI / Al3B 4 sC 2 composite thus obtained is observed under SEM (single figure). The white phase corresponds to the aluminum matrix and the black particles correspond to the reinforcement phase Al3B 4 sC 2 . It is found that the reinforcements are homogeneously dispersed in the matrix and have a size of between 200 nm and 5 μιη (average size of about 700 nm).
Le procédé objet de l'invention permet de créer une interface entre un matrice et un renfort qui soit mécaniquement forte, mais sans conduire à la décomposition du renfort et à la création de phases secondaires délétères pour les propriétés du composite. En effet, lors de la synthèse réactive entre AIB2 et le graphite (C), il y a très peu de phases mineures qui se créent et le composite comporte donc essentiellement une phase d'AI (formant la matrice) et une phase d'Al3B48C2 (renfort), les phases mineures étant présentes en quantités minimes. The method of the invention makes it possible to create an interface between a matrix and a reinforcement which is mechanically strong, but without leading to the decomposition of the reinforcement and the creation of deleterious secondary phases for the properties of the composite. Indeed, during the reactive synthesis between AIB 2 and graphite (C), there are very few minor phases are formed and the composite thus essentially comprises a phase of Al (the matrix) and a phase of Al3B 4 8C 2 (reinforcement), the minor phases being present in minimal amounts.
Au final, le procédé selon l'invention apporte une nouvelle voie de synthèse pour produire de manière simple et en quantité des matériaux composites à matrice Al renforcée par des particules d'un carbure mixte de bore (B) et d'aluminium (Al) dont les propriétés sont proches de celles d'un renfort en B4C. Finally, the process according to the invention provides a new synthetic route for producing, in a simple manner and in quantity, Al-matrix composite materials reinforced with particles of a mixed boron (B) and aluminum (Al) carbide. whose properties are close to those of a B 4 C reinforcement.
REFERENCE CITEE REFERENCE CITEE
[1] US 11/033,099 [1] US 11/033,099

Claims

REVENDICATIONS
1. Procédé de fabrication d'une pièce en un matériau composite AI/Al3B48C2 comprenant une matrice en aluminium dans laquelle sont dispersées des particules d'un carbure mixte de formule chimique Al3B4sC2, ledit procédé comprenant les étapes suivantes : 1. A method of manufacturing a piece of composite material AI / Al3B 4 8C 2 comprising an aluminum matrix having dispersed therein particles of a mixed carbide of chemical formula 4 Al3B sC 2, said method comprising the steps of:
a) la mise en place d'une poudre de formule chimique AIB2 dans la cavité d'un creuset en graphite ; a) the establishment of a powder of chemical formula AIB 2 in the cavity of a graphite crucible;
b) la fermeture de la cavité par un élément en graphite ; c) le chauffage du creuset à une température au moins égale à 960°C et inférieure ou égale à 1400°C pour obtenir la formation de précipités du carbure mixte de formule chimique Al3B4sC2 dans de l'aluminium liquide ; b) closing the cavity by a graphite element; c) heating the crucible at a temperature of at least 960 ° C and less than or equal to 1400 ° C to obtain the formation of mixed carbide precipitates of chemical formula Al3B 4 sC 2 in liquid aluminum;
d) le refroidissement du creuset pour solidifier l'aluminium liquide ; e) l'élimination du creuset ;  d) cooling the crucible to solidify the liquid aluminum; e) elimination of the crucible;
moyennant quoi on obtient la pièce en matériau composite AI/Al3B48C2. whereby the composite material part AI / Al3B 4 8C 2 is obtained.
2. Procédé selon la revendication 1, dans l'élément en graphite serva nt à fermer la cavité est un piston en graphite. 2. Method according to claim 1, in the graphite element used to close the cavity is a graphite piston.
3. Procédé selon la revendication 1 ou la revendication 2, dans lequel la poudre est mise en place dans le creuset sous une forme compressée. 3. The method of claim 1 or claim 2, wherein the powder is placed in the crucible in a compressed form.
4. Procédé selon la revendication 1 ou la revendication 2, dans lequel la poudre est mise en place dans le creuset sous une forme pulvérulente et l'étape b) comprend de plus une compression de la poudre. 4. A process according to claim 1 or claim 2, wherein the powder is placed in the crucible in powder form and step b) further comprises compression of the powder.
5. Procédé selon la revendication 4 lorsqu'elle dépend de la revendication 2, dans lequel la compression de la poudre et la fermeture de la cavité du creuset sont obtenues par l'utilisation d'un piston en graphite. 5. The method of claim 4 when dependent on claim 2, wherein the compression of the powder and the closure of the crucible cavity are obtained by the use of a graphite piston.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel, à l'étape c), le creuset est chauffé à une température allant de 1000°C à 1400°C pendant une durée allant de 5 minutes à 30 minutes. 6. Process according to any one of claims 1 to 5, wherein, in step c), the crucible is heated to a temperature ranging from 1000 ° C to 1400 ° C for a period ranging from 5 minutes to 30 minutes .
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le refroidissement à l'étape d) comprend une descente en température avec une vitesse supérieure ou égale à 10°C/s jusqu'à atteindre 600°C. The process according to any one of claims 1 to 6, wherein the cooling in step d) comprises a descent in temperature with a speed greater than or equal to 10 ° C / s until reaching 600 ° C.
EP16741604.9A 2015-07-20 2016-07-19 Process for manufacturing an al/al3b48c3 composite Not-in-force EP3325681B1 (en)

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