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EP1147237A1 - Hypereutectic aluminium-silicon alloy product for semisolid forming - Google Patents

Hypereutectic aluminium-silicon alloy product for semisolid forming

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Publication number
EP1147237A1
EP1147237A1 EP00900600A EP00900600A EP1147237A1 EP 1147237 A1 EP1147237 A1 EP 1147237A1 EP 00900600 A EP00900600 A EP 00900600A EP 00900600 A EP00900600 A EP 00900600A EP 1147237 A1 EP1147237 A1 EP 1147237A1
Authority
EP
European Patent Office
Prior art keywords
eutectic
silicon
boron
aluminum
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00900600A
Other languages
German (de)
French (fr)
Other versions
EP1147237B1 (en
Inventor
Gérard Laslaz
François COSSE
Michel Garat
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.)
Rio Tinto France SAS
Original Assignee
Aluminium Pechiney SA
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.)
Filing date
Publication date
Application filed by Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Publication of EP1147237A1 publication Critical patent/EP1147237A1/en
Application granted granted Critical
Publication of EP1147237B1 publication Critical patent/EP1147237B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • 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
    • C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys

Definitions

  • Hypereutectic aluminum-silicon alloy product for shaping in semi-solid state
  • the invention relates to Al-Si alloy products, with possibly other addition elements, in which the silicon content is such that it is equal to or greater than the composition of the eutectic (11.7% in the case where there is no other element of addition).
  • These products such as billets, then cut into pieces corresponding to the quantity of metal necessary for the part to be manufactured, or forging blanks, are intended to be reheated in the semi-solid state, that is to say say at a temperature between the solidus and the liquidus of the alloy, to be shaped, in particular by forging or injection under pressure.
  • Aluminum-silicon alloys possibly comprising other addition elements such as copper, magnesium, manganese, zinc, nickel or cobalt, and in which the silicon content is equal to or greater than that of eutectics are used for the production of molded parts with low thermal expansion and good resistance to friction, for example pistons and liners of internal combustion engines, or parts of braking or clutch systems. on the other hand, are quite difficult to mold and to machine, and all the more so as the silicon content is high.
  • the parts obtained show good metallurgical health, with no shrinkage and segregation and the process allows high rates well suited to large series in the automotive industry.
  • Patent application JP 08-323461 (Asahi Tec) describes a process for forming a semi-solid state of a hypereutectic AlSi alloy, in which the shear intended to improve the rheology and the filling of the mold are concomitant, so that the incoming metal introduces stirring which leads to a thixotropic structure and reduces the segregation of the primary silicon crystals.
  • the article by I. Diewwanit and MC Flemings "Semi-Solid Forming of Hypereutectic Al-Si Alloys" Light Metals 1996, The Minerais, Metals & Materials Society, pp.
  • the Applicant has discovered that it is possible to obtain, for eutectic or hypereutectic AlSi alloys, rheological properties in the semi-solid state very favorable for shaping by thixoforming starting from a solid product having a particular solidification structure. , obtained in a simple way without mechanical or electromagnetic stirring.
  • the subject of the invention is a product made of an eutectic or hypereutectic aluminum-silicon alloy suitable for thixoforming, comprising (by weight) from 10 to 30% of silicon and optionally copper ( ⁇ 10%), magnesium ( ⁇ 3%), manganese ( ⁇ 2%), iron ( ⁇ 2%), nickel ( ⁇ 4%), cobalt ( ⁇ 3%) and other elements ( ⁇ 0.5% each and 1% in total), whose microstructure in the raw casting state consists of primary silicon crystals, equiaxial type aluminum dendrites and less than 4 mm in size, and an eutectic consisting of eutectic silicon grains and eutectic aluminum less than 4 mm in size. It also relates to a process for obtaining this microstructure consisting in adding to the alloy from 50 to 2000 ppm (by weight) of boron, the amount added being in excess compared to that strictly necessary for the precipitation of impurities.
  • the solidification structure of the hypereutectic AlSi alloys comprises: a) primary silicon particles, the size of which can be refined, in particular by adding 20 to 500 ppm of phosphorus, b ) aluminum dendrites formed at the start of the eutectic plateau, which often reach sizes greater than 5 mm, c) an eutectic consisting of eutectic silicon grains and eutectic aluminum grains and, where appropriate, of intermetallic phases making intervene the other alloying elements such as Cu, Mg or Ni.
  • the size of the eutectic aluminum grains is correlated with that of the dendrites and substantially of the same value. Can reveal the presence and size of these grains * eutectic aluminum columnar appearance by etching the sample ferric chloride or three-acid.
  • the Applicant has found that when either the aluminum dendrites or the eutectic aluminum grains have a columnar (or basaltic) shape and a size greater than 4 mm, the product reheated in the semi-solid state to 'at a liquid fraction rate of between 20 and 60% had a poorly globulated structure, the eutectic aluminum grains having an elongated shape leading to a rheology unfavorable for shaping under good conditions.
  • the dendrites and the eutectic aluminum grains had an equiaxial type structure, with a size less than 4 mm, the structure of the product reheated in the semi-solid state is well globulated, which leads to a rheology favorable for easy shaping of the part to be produced and good metallurgical quality of this part.
  • the structure according to the invention is found in the entire piece or blank to be heated. Indeed, if this structure only exists in one part, the heterogeneity of the structure leads to difficulties during shaping.
  • An effective means of obtaining, in a reliable and repetitive manner, and without resorting to mechanical or electromagnetic stirring, the structure according to the invention is to add to the liquid metal intended to be cast in the form of a billet or a blank of 0.005 at 0.2%, and preferably from 0.01 to 0.05%, of boron. Boron is used in the usual way for the purification of aluminum, so as to precipitate impurities such as Ti, Zr, Mn or V in the form of intermetallic borides.
  • Titanium and boron master alloys such as 1 ⁇ -T5B, are also usually used to refine the grain of the aluminum, by formation of TiB 2 particles; in these alloys the titanium is in excess relative to the stoichiometric quantity necessary for the formation of TiB and the total boron content does not exceed 50 ppm.
  • the boron added according to the invention is in excess of at least 0.005% relative to the stoichiometric quantity strictly necessary for elimination of impurities in the form of intermetallic compounds.
  • the addition of boron can be in the form of master alloys Al-B (for example the alloys A-B3 or A-B6). Si-B or Al-Si-B (e.g., the alloy A-S10B3). It can also be done in the form of a fluoborate flux.
  • the products according to the invention can be used for all the usual applications of eutectic or hypereutectic alloys up to 30% of silicon, in particular parts subjected to wear-friction, such as drums and brake discs, cylinders or liners of engines. or compressors, pistons and gearbox forks.
  • Alloys A-S17U4G containing (by weight) 17% Si, 4% Cu and 0.6% Mg were developed, with the addition of 100 ppm of phosphorus to refine the primary silicon grains.
  • Alloy A contained no other addition alloy B was produced with the addition of 0.15% titanium and 0.3% AT5B, the master alloy with 5% titanium and 1% boron.
  • Alloy C according to the invention was prepared with the addition of 0.03%> of boron. The metal was cast in the form of 75 mm diameter billets by semi-continuous casting under load, without mechanical or electromagnetic stirring.
  • the examination of a section reveals a structure with dendrites and aluminum grains of equiaxial appearance, testifying to a homogeneous germination, of size between 0.2 and 2 mm. After reheating in the semi-solid state, the eutectic aluminum is perfectly globulated, and the rheology test is systematically good.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Continuous Casting (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Forging (AREA)
  • Soft Magnetic Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

This invention relates to a eutectic or hypereutectic aluminium-silicon alloy product suitable for thixoforming, comprising (by weight) 10 to 30% silicon and, if applicable, copper (<10%), magnesium (<3%), manganese (<2%), iron (<2%), nickel (<4%), cobalt (<3%) and other elements (<0.5% each and 1% in total), the microstructure of which is composed of primary silicon crystals, equiaxed type aluminium dendrites less than 4 mm in size and a eutectic composed of eutectic silicon grains and eutectic aluminium grains less than 4 mm in size.

Description

Produit en alliage aluminium-silicium hypereutectique pour mise en forme à l'état semi-solide Hypereutectic aluminum-silicon alloy product for shaping in semi-solid state
Domaine techniqueTechnical area
L'invention concerne des produits en alliage Al-Si, avec éventuellement d'autres éléments d'addition, dans lesquels la teneur en silicium est telle qu'elle soit égale ou supérieure à la composition de l'eutectique (11,7% dans le cas où il n'y a pas d'autre élément d'addition). Ces produits, tels que des billettes, découpées ensuite en lopins correspondant à la quantité de métal nécessaire à la pièce à fabriquer, ou des ébauches de forge, sont destinés à être réchauffés à l'état semi-solide, c'est-à-dire à une température comprise entre le solidus et le liquidus de l'alliage, pour être mis en forme, notamment par forgeage ou injection sous pression.The invention relates to Al-Si alloy products, with possibly other addition elements, in which the silicon content is such that it is equal to or greater than the composition of the eutectic (11.7% in the case where there is no other element of addition). These products, such as billets, then cut into pieces corresponding to the quantity of metal necessary for the part to be manufactured, or forging blanks, are intended to be reheated in the semi-solid state, that is to say say at a temperature between the solidus and the liquidus of the alloy, to be shaped, in particular by forging or injection under pressure.
Etat de la techniqueState of the art
Les" alliages aluminium-silicium, comportant éventuellement d'autres éléments d'addition tels que le cuivre, le magnésium, le manganèse, le zinc, le nickel ou le cobalt, et dans lesquels la teneur en silicium est égale ou supérieure à celle de l'eutectique, sont utilisés pour la fabrication de pièces moulées présentant une faible dilatation thermique et une bonne résistance au frottement, par exemple des pistons et des chemises de moteurs à combustion interne, ou pièces de systèmes de freinage ou d'embrayage. Ces alliages sont par contre assez difficiles à mouler et à usiner, et ce d'autant plus que la teneur en silicium est élevée. " Aluminum-silicon alloys, possibly comprising other addition elements such as copper, magnesium, manganese, zinc, nickel or cobalt, and in which the silicon content is equal to or greater than that of eutectics are used for the production of molded parts with low thermal expansion and good resistance to friction, for example pistons and liners of internal combustion engines, or parts of braking or clutch systems. on the other hand, are quite difficult to mold and to machine, and all the more so as the silicon content is high.
Il est donc intéressant de disposer d'un procédé qui évite la fusion complète de l'alliage et conduise à une forme aussi proche que possible de la forme finale désirée pour la pièce fabriquée. C'est le cas de la mise en forme à l'état semi-solide ou thixoformage. Cette technique s'est développée depuis une vingtaine d'années à la suite des travaux du Pr Flemings au MIT, en particulier pour les alliages d'aluminium. Elle consiste à couler des demi-produits tels que des billettes en leur appliquant une force de cisaillement, par exemple par agitation mécanique ou brassage électromagnétique, de manière à transformer la structure de solidification dendritique en structure globulaire, à réchauffer des morceaux de ces demi-produits à l'état semi-solide et à les mettre en forme par injection sous pression ou forgeage.It is therefore advantageous to have a process which avoids the complete melting of the alloy and leads to a shape as close as possible to the final shape desired for the manufactured part. This is the case with shaping in the semi-solid state or thixoforming. This technique has developed over the last twenty years following the work of Professor Flemings at MIT, in particular for alloys aluminum. It consists in pouring semi-finished products such as billets by applying a shearing force to them, for example by mechanical agitation or electromagnetic stirring, so as to transform the dendritic solidification structure into a globular structure, to heat pieces of these semi- semi-solid products and shaping them by pressure injection or forging.
Les pièces obtenues présentent une bonne santé métallurgique, avec une absence de retassure et de ségrégation et le procédé permet des cadences élevées bien adaptées aux grandes séries de l'industrie automobile.The parts obtained show good metallurgical health, with no shrinkage and segregation and the process allows high rates well suited to large series in the automotive industry.
La majeure partie des applications industrielles utilisent l'alliage AS7G à 7% de silicium (A356 et 357 selon la désignation de l'Aluminum Association). Le thixoformage d'alliages d'aluminium hypereutectiques est décrit dans la demande de brevet EP 0572683 de la société Honda Giken. Cette demande préconise de partir d'un matériau solide dans lequel la taille de grain maximale des cristaux de silicium primaire est inférieure à 100 μm, ce qui évite une usure trop rapide de l'attaque et de l'empreinte du moule d'injection. La demande ne donne aucune indication sur le procédé de coulée conduisant à une telle structure.Most industrial applications use the AS7G 7% silicon alloy (A356 and 357 according to the designation of the Aluminum Association). The thixoforming of hypereutectic aluminum alloys is described in patent application EP 0572683 from the company Honda Giken. This application recommends starting from a solid material in which the maximum grain size of the primary silicon crystals is less than 100 μm, which avoids too rapid wear of the attack and the imprint of the injection mold. The application gives no indication of the casting process leading to such a structure.
La demande de brevet JP 08-323461 (Asahi Tec) décrit un procédé de mise en forme à l'état semi-solide d'un alliage AlSi hypereutectique, dans lequel le cisaillement destiné à améliorer la rhéologie et le remplissage du moule sont concomitants, de sorte que le métal entrant introduit une agitation qui conduit à une structure thixotrope et réduit la ségrégation des cristaux de silicium primaire. L'article de I. Diewwanit et M.C. Flemings " Semi-Solid Forming of Hypereutectic Al-Si Alloys " Light Metals 1996, The Minerais, Metals & Materials Society, pp. 787-793, fait dans son introduction un exposé complet de la bibliographie sur la mise en forme à l'état semi-solide des alliages AlSi hypereutectiques, et décrit des essais de rhéomoulage avec agitation mécanique. Aucun des moyens décrits ne permet d'améliorer de manière simple l'aptitude au thixoformage des alliages d'aluminium hypereutectiques. Par ailleurs, le brevet US 5701942 (Ube Industries) décrit un procédé de mise en œuvre à l'état semi-solide d'alliages d'aluminium hypoeutectiques. Les exemples montrent différentes compositions avec des teneurs en silicium allant de 3 à 1 1%, et une composition avec 7% Si, 0J5% Ti et 0,005% B, ce qui représente un large excès de Ti par rapport à la proportion stoechiométrique correspondant à TiB2.Patent application JP 08-323461 (Asahi Tec) describes a process for forming a semi-solid state of a hypereutectic AlSi alloy, in which the shear intended to improve the rheology and the filling of the mold are concomitant, so that the incoming metal introduces stirring which leads to a thixotropic structure and reduces the segregation of the primary silicon crystals. The article by I. Diewwanit and MC Flemings "Semi-Solid Forming of Hypereutectic Al-Si Alloys" Light Metals 1996, The Minerais, Metals & Materials Society, pp. 787-793, introduces in its introduction a complete bibliography on the shaping in the semi-solid state of AlSi hypereutectic alloys, and describes rheomolding tests with mechanical agitation. None of the means described makes it possible to improve in a simple manner the suitability for thixoforming of hypereutectic aluminum alloys. Furthermore, US Pat. No. 5,701,942 (Ube Industries) describes a process for using hypoeutectic aluminum alloys in the semi-solid state. The examples show different compositions with silicon contents ranging from 3 to 11%, and a composition with 7% Si, 0J5% Ti and 0.005% B, which represents a large excess of Ti compared to the stoichiometric proportion corresponding to TiB 2 .
Objet de l'inventionSubject of the invention
La demanderesse a découvert qu'on pouvait obtenir, pour les alliages AlSi eutectiques ou hypereutectiques, des propriétés rhéologiques à l'état semi-solide très favorables à la mise en forme par thixoformage en partant d'un produit solide présentant une structure de solidification particulière, obtenue de manière simple sans brassage mécanique ou électromagnétique.The Applicant has discovered that it is possible to obtain, for eutectic or hypereutectic AlSi alloys, rheological properties in the semi-solid state very favorable for shaping by thixoforming starting from a solid product having a particular solidification structure. , obtained in a simple way without mechanical or electromagnetic stirring.
L'invention a pour objet un produit en alliage aluminium-silicium eutectique ou hypereutectique apte au thixoformage, comportant (en poids) de 10 à 30% de silicium et éventuellement du cuivre (< 10%), du magnésium (< 3%), du manganèse (< 2%), du fer (< 2%), du nickel (< 4%), du cobalt (< 3%) et d'autres éléments (< 0,5% chacun et 1% au total), dont la microstructure à l'état brut de coulée est constituée de cristaux de silicium primaire, de dendrites d'aluminium de type équiaxe et de taille inférieure à 4 mm, et d'un eutectique constitué de grains de silicium eutectique et de grains d'aluminium eutectique de taille inférieure à 4 mm. Elle a également pour objet un procédé pour obtenir cette microstructure consistant à ajouter à l'alliage de 50 à 2000 ppm (en poids) de bore, la quantité ajoutée étant en excès par rapport à celle strictement nécessaire à la précipitation des impuretés.The subject of the invention is a product made of an eutectic or hypereutectic aluminum-silicon alloy suitable for thixoforming, comprising (by weight) from 10 to 30% of silicon and optionally copper (<10%), magnesium (<3%), manganese (<2%), iron (<2%), nickel (<4%), cobalt (<3%) and other elements (<0.5% each and 1% in total), whose microstructure in the raw casting state consists of primary silicon crystals, equiaxial type aluminum dendrites and less than 4 mm in size, and an eutectic consisting of eutectic silicon grains and eutectic aluminum less than 4 mm in size. It also relates to a process for obtaining this microstructure consisting in adding to the alloy from 50 to 2000 ppm (by weight) of boron, the amount added being in excess compared to that strictly necessary for the precipitation of impurities.
Description de l'inventionDescription of the invention
La structure de solidification des alliages AlSi hypereutectiques, telle qu'on peut l'observer sur une coupe métallographique, comprend : a) des particules de silicium primaire dont la taille peut être affinée, notamment par ajout de 20 à 500 ppm de phosphore, b) des dendrites d'aluminium formées en début de palier eutectique, qui atteignent souvent des tailles supérieures à 5 mm, c) un eutectique constitué de grains de silicium eutectique et de grains d'aluminium eutectique et, le cas échéant, de phases intermétalliques faisant intervenir les autres éléments d'alliage tels que Cu, Mg ou Ni. La taille des grains d'aluminium eutectique est corrélée à celle des dendrites et sensiblement de la même valeur. On peut révéler la présence et la taille de ces grains d*aluminium eutectique d'aspect colonnaire par attaque de l'échantillon au chlorure ferrique ou aux trois acides.The solidification structure of the hypereutectic AlSi alloys, as can be seen on a metallographic section, comprises: a) primary silicon particles, the size of which can be refined, in particular by adding 20 to 500 ppm of phosphorus, b ) aluminum dendrites formed at the start of the eutectic plateau, which often reach sizes greater than 5 mm, c) an eutectic consisting of eutectic silicon grains and eutectic aluminum grains and, where appropriate, of intermetallic phases making intervene the other alloying elements such as Cu, Mg or Ni. The size of the eutectic aluminum grains is correlated with that of the dendrites and substantially of the same value. Can reveal the presence and size of these grains * eutectic aluminum columnar appearance by etching the sample ferric chloride or three-acid.
La demanderesse a constaté que lorsque soit les dendrites d'aluminium, soit les grains d'aluminium eutectique, présentaient une forme de type colonnaire (ou basaltique) et une taille supérieure à 4 mm, le produit réchauffé à l'état semi-solide jusqu'à un taux de fraction liquide compris entre 20 et 60% présentait une structure mal globulisée, les grains d'aluminium eutectique présentant une forme allongée conduisant à une rhéologie défavorable à la mise en forme dans de bonnes conditions. Par contre, si les dendrites et les grains d'aluminium eutectique présentaient une structure de type équiaxe, avec une taille inférieure à 4 mm, la structure du produit réchauffé à l'état semi-solide est bien globulisée, ce qui conduit à une rhéologie favorable à une mise en forme aisée de la pièce à réaliser et une bonne qualité métallurgique de cette pièce.The Applicant has found that when either the aluminum dendrites or the eutectic aluminum grains have a columnar (or basaltic) shape and a size greater than 4 mm, the product reheated in the semi-solid state to 'at a liquid fraction rate of between 20 and 60% had a poorly globulated structure, the eutectic aluminum grains having an elongated shape leading to a rheology unfavorable for shaping under good conditions. On the other hand, if the dendrites and the eutectic aluminum grains had an equiaxial type structure, with a size less than 4 mm, the structure of the product reheated in the semi-solid state is well globulated, which leads to a rheology favorable for easy shaping of the part to be produced and good metallurgical quality of this part.
Il est important que la structure selon l'invention se retrouve dans la totalité du lopin ou de l'ébauche à réchauffer. En effet, si cette structure n'existe que dans une partie, l'hétérogénéité de la structure conduit à des difficultés lors de la mise en forme. Un moyen efficace d'obtenir, de manière fiable et répétitive, et sans recourir à un brassage mécanique ou électromagnétique, la structure selon l'invention est d'ajouter au métal liquide destiné à être coulé sous forme de billette ou d'ébauche de 0,005 à 0,2%, et de préférence de 0,01 à 0,05%, de bore. Le bore est utilisé de manière habituelle pour la purification de l'aluminium, de manière à précipiter les impuretés telles que Ti, Zr, Mn ou V sous forme de borures intermétalliques. On utilise aussi habituellement des alliages-mères au titane et au bore, comme 1Α-T5B, pour affiner le grain de l'aluminium, par formation de particules de TiB2 ; dans ces alliages le titane est en excès par rapport à la quantité stoechiométrique nécessaire à la formation de TiB et la teneur totale en bore ne dépasse pas 50 ppm.It is important that the structure according to the invention is found in the entire piece or blank to be heated. Indeed, if this structure only exists in one part, the heterogeneity of the structure leads to difficulties during shaping. An effective means of obtaining, in a reliable and repetitive manner, and without resorting to mechanical or electromagnetic stirring, the structure according to the invention is to add to the liquid metal intended to be cast in the form of a billet or a blank of 0.005 at 0.2%, and preferably from 0.01 to 0.05%, of boron. Boron is used in the usual way for the purification of aluminum, so as to precipitate impurities such as Ti, Zr, Mn or V in the form of intermetallic borides. Titanium and boron master alloys, such as 1Α-T5B, are also usually used to refine the grain of the aluminum, by formation of TiB 2 particles; in these alloys the titanium is in excess relative to the stoichiometric quantity necessary for the formation of TiB and the total boron content does not exceed 50 ppm.
Il est indispensable que le bore ajouté selon l'invention soit en excès d'au moins 0.005% par rapport à la quantité stoechiométrique strictement nécessaire à l'élimination des impuretés sous forme de composés intermétalliques. L'ajout de bore peut se faire sous forme d'alliages-mères Al-B (par exemple les alliages A-B3 ou A-B6). Si-B ou Al-Si-B (par exemple l'alliage A-S10B3). Il peut se faire également sous forme d'un flux au fluoborate. Les produits selon l'invention peuvent être utilisés pour toutes les applications habituelles des alliages eutectiques ou hypereutectiques jusqu'à 30% de silicium, notamment les pièces sollicitées en usure-frottement, comme les tambours et disques de freins, les cylindres ou chemises de moteurs ou de compresseurs, les pistons et les fourchettes de boites de vitesse.It is essential that the boron added according to the invention is in excess of at least 0.005% relative to the stoichiometric quantity strictly necessary for elimination of impurities in the form of intermetallic compounds. The addition of boron can be in the form of master alloys Al-B (for example the alloys A-B3 or A-B6). Si-B or Al-Si-B (e.g., the alloy A-S10B3). It can also be done in the form of a fluoborate flux. The products according to the invention can be used for all the usual applications of eutectic or hypereutectic alloys up to 30% of silicon, in particular parts subjected to wear-friction, such as drums and brake discs, cylinders or liners of engines. or compressors, pistons and gearbox forks.
ExemplesExamples
On a élaboré des alliages A-S17U4G contenant (en poids) 17% Si, 4% Cu et 0,6% Mg, avec addition de 100 ppm de phosphore pour affiner les grains de silicium primaire. L'alliage A ne contenait aucune autre addition, l'alliage B a été élaboré avec addition de 0,15% de titane et 0,3% d'AT5B, alliage-mère à 5% de titane et 1% de bore. L'alliage C selon l'invention a été élaboré avec addition de 0,03%> de bore. Le métal a été coulé sous forme de billettes de diamètre 75 mm par coulée semi- continue en charge, sans brassage mécanique ni électromagnétique. L'examen d'une coupe métallographique d'une billette d'alliage A a montré, soit pour toute la section de la billette, soit au moins sur la partie la plus proche du périmètre, une structure comportant des dendrites d'aluminium et des grains d'aluminium eutectique de forme colonnaire (ou basaltique) de taille comprise entre 3 et 10 mm. Après réchauffage à l'état semi-solide, à un taux de fraction liquide de l'ordre de 40%, on observe que l'aluminium eutectique n'est pas globulisé. Le test de rhéologie révèle ce métal inapte au formage semi-solide. Même si la partie centrale de la billette présentait une structure moins défavorable, le remplissage du moule au thixoformage présentait des difficultés dues à l'hétérogénéité de la rhéologie entre le centre et le bord. L'examen d'une coupe de billette d'alliage B montre une structure mixte, plutôt colonnaire vers l'extérieur de la billette et plutôt équiaxe vers le centre, la taille des dendrites et des grains d'aluminium eutectique variant entre 0,2 et 10 mm. Après réchauffage à l'état semi-solide, on obtient une structure partiellement globulisée.Alloys A-S17U4G containing (by weight) 17% Si, 4% Cu and 0.6% Mg were developed, with the addition of 100 ppm of phosphorus to refine the primary silicon grains. Alloy A contained no other addition, alloy B was produced with the addition of 0.15% titanium and 0.3% AT5B, the master alloy with 5% titanium and 1% boron. Alloy C according to the invention was prepared with the addition of 0.03%> of boron. The metal was cast in the form of 75 mm diameter billets by semi-continuous casting under load, without mechanical or electromagnetic stirring. Examination of a metallographic section of a billet of alloy A has shown, either for the entire section of the billet, or at least on the part closest to the perimeter, a structure comprising aluminum dendrites and columnar (or basaltic) eutectic aluminum grains between 3 and 10 mm in size. After reheating in the semi-solid state, at a rate of liquid fraction of the order of 40%, it is observed that the eutectic aluminum is not globulated. The rheology test reveals this metal unsuitable for semi-solid forming. While the central part of the billet showed a less unfavorable structure, filling the mold Thixoforming presented difficulties due to the heterogeneity of the rheology between the center and the edge. Examination of a billet B alloy cut shows a mixed structure, rather columnar towards the outside of the billet and rather equiaxed towards the center, the size of the dendrites and of the eutectic aluminum grains varying between 0.2 and 10 mm. After reheating in the semi-solid state, a partially globularized structure is obtained.
Comme dans le cas précédent, l'hétérogénéité de la structure entraîne des variations de la rhéologie, qui conduisent à des difficultés dans le remplissage du moule.As in the previous case, the heterogeneity of the structure leads to variations in the rheology, which lead to difficulties in filling the mold.
Pour la billette en alliage C selon l'invention, l'examen d'une coupe révèle une structure avec des dendrites et des grains d'aluminium d'aspect équiaxe, témoignant d'une germination homogène, de taille comprise entre 0,2 et 2 mm. Après réchauffage à l'état semi-solide, l'aluminium eutectique est parfaitement globulisé, et le test de rhéologie est systématiquement bon. For the billet of alloy C according to the invention, the examination of a section reveals a structure with dendrites and aluminum grains of equiaxial appearance, testifying to a homogeneous germination, of size between 0.2 and 2 mm. After reheating in the semi-solid state, the eutectic aluminum is perfectly globulated, and the rheology test is systematically good.

Claims

Revendications claims
1. Produit en alliage aluminium-silicium eutectique ou hypereutectique apte au thixoformage, comportant (en poids) de 10 à 30% de silicium et éventuellement du cuivre (< 10%), du magnésium (< 3%), du manganèse (< 2%), du fer (< 2%), du nickel (< 4%), du cobalt (< 3%) et d'autres éléments (< 0,5% chacun et 1% au total), dont la microstructure est constituée de cristaux de silicium primaire, de dendrites d'aluminium de taille inférieure à 4 mm, et d'un eutectique constitué de grains de silicium eutectique et de grains d'aluminium eutectique de taille inférieure à 4 mm.1. Product made of an eutectic or hypereutectic aluminum-silicon alloy suitable for thixoforming, comprising (by weight) from 10 to 30% of silicon and possibly copper (<10%), magnesium (<3%), manganese (<2 %), iron (<2%), nickel (<4%), cobalt (<3%) and other elements (<0.5% each and 1% in total), of which the microstructure is made up primary silicon crystals, aluminum dendrites less than 4 mm in size, and an eutectic consisting of eutectic silicon grains and eutectic aluminum grains less than 4 mm in size.
2. Produit selon la revendication 1 , caractérisé en ce qu'il contient de 0,002 à 0,05% de phosphore.2. Product according to claim 1, characterized in that it contains from 0.002 to 0.05% of phosphorus.
3. Produit selon la revendication 1, caractérisé en ce qu'il contient de 0,005 à 0,2% de bore.3. Product according to claim 1, characterized in that it contains from 0.005 to 0.2% of boron.
4. Produit selon la revendication 3, caractérisé en ce qu'il contient au moins 0,005% de bore non associé sous forme de composé intermétallique à l'un au moins des éléments Ti, Zr, Mn ou V.4. Product according to claim 3, characterized in that it contains at least 0.005% of boron not associated in the form of an intermetallic compound with at least one of the elements Ti, Zr, Mn or V.
5. Produit selon l'une des revendications 3 ou 4, caractérisé en ce qu'il contient de 0,01 à 0,05% de bore.5. Product according to one of claims 3 or 4, characterized in that it contains 0.01 to 0.05% boron.
6. Procédé de fabrication d'un produit selon la revendication 3, consistant à ajouter à l'alliage liquide servant à l'élaboration du produit une quantité de bore en excès par rapport à celle nécessaire à l'élimination des impuretés.6. A method of manufacturing a product according to claim 3, comprising adding to the liquid alloy used for the preparation of the product an amount of excess boron relative to that necessary for the removal of impurities.
7. Procédé selon la revendication 4, caractérisé en ce que le bore est introduit dans l'alliage liquide sous forme d'alliage-mère A1B, SiB ou AlSiB. Procédé selon la revendication 5, caractérisé en ce que le bore est introduit dans l'alliage liquide sous forme de flux à base de fluoborate. 7. Method according to claim 4, characterized in that the boron is introduced into the liquid alloy in the form of master alloy A1B, SiB or AlSiB. A method according to claim 5, characterized in that the boron is introduced into the liquid alloy in the form of fluoborate based flux.
EP00900600A 1999-01-21 2000-01-18 Hypereutectic aluminium-silicon alloy product for semisolid forming Expired - Lifetime EP1147237B1 (en)

Applications Claiming Priority (3)

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FR9900787 1999-01-21
FR9900787A FR2788788B1 (en) 1999-01-21 1999-01-21 HYPEREUTECTIC ALUMINUM-SILICON ALLOY PRODUCT FOR SHAPING IN SEMI-SOLID CONDITION
PCT/FR2000/000095 WO2000043559A1 (en) 1999-01-21 2000-01-18 Hypereutectic aluminium-silicon alloy product for semisolid forming

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