EP1680246B1 - Procede de production de materiaux composites a base de matrice metallique - Google Patents

Procede de production de materiaux composites a base de matrice metallique Download PDF

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Publication number
EP1680246B1
EP1680246B1 EP04765979A EP04765979A EP1680246B1 EP 1680246 B1 EP1680246 B1 EP 1680246B1 EP 04765979 A EP04765979 A EP 04765979A EP 04765979 A EP04765979 A EP 04765979A EP 1680246 B1 EP1680246 B1 EP 1680246B1
Authority
EP
European Patent Office
Prior art keywords
composite material
metal
magnesium
matrix
matrix composite
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.)
Expired - Fee Related
Application number
EP04765979A
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German (de)
English (en)
Other versions
EP1680246A1 (fr
Inventor
Florian Moll
Lutz Oemisch
Ulrich Bischofberger
Karl Ulrich Prof. Dr.-Ing. Kainer
Norbert Hort
Hajo Dieringa
Hagen Frank
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.)
Mahle GmbH
Original Assignee
Mahle GmbH
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Filing date
Publication date
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Expired - Fee Related legal-status Critical Current
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • 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
    • C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • 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
    • C22C23/00—Alloys based on magnesium
    • 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
    • C22C32/0078—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 silicides

Definitions

  • the present invention relates to a method for the production of metal-matrix composite materials comprising at least one portion of magnesium or a magnesium alloy and at least one production step in which a thixomolding takes place.
  • the material magnesium can not readily be used for certain applications, such as pistons in motor vehicle engines or other engine components, in particular of engines.
  • the properties mentioned can be positively influenced by the material is reinforced by means of a second, usually much firmer and harder phase-usually find ceramic or carbon-based short or long fibers or particles.
  • These can be introduced in a melt-metallurgical production either in the form of a porous shaped body (so-called preform), which is infiltrated with liquid molten metal, or in the case of particles also by stirring into the metallic matrix.
  • Another way to reinforce a metallic material by fibers or particles consists in the self-or "in situ" formation of the reinforcing component.
  • metallic composite materials can also be produced by powder metallurgy.
  • Composite material of this type can be cast directly in the form of castings or ingots. In the in-situ process, the composite is formed by a reaction between two or three a plurality of alloying elements of the metallic matrix or phases of the overall system, usually forming a new, usually intermetallic phase.
  • the DE 101 35 198 A1 describes a process for the production of magnesium alloys by thixomolding, which may also contain a proportion of silicon among other elements.
  • the metallic material is fed as granules to the thixomolding machine and moved within a heated cylinder by a transport screw in the direction of the spray nozzle.
  • the temperature which lies between the liquidus and solidus temperature of the metal, this partially liquefies, while the remaining solid content forms globular
  • the behavior of the thixotropic material is pseudoplastic, that is, the viscosity decreases with increasing shear.
  • the Thixomolding is particularly suitable for the production of very thin-walled components with high dimensional stability, since it hardly comes to shrinkage and distortion due to the favorable temperature level between liquidus and solidus
  • the infiltration ability of preforms with high fiber and particle contents in classical die casting is not readily given, preferably the method of squeeze casting is used for this purpose, for which in turn special casting plants are necessary.
  • the difficulties that can arise in die-casting infiltration are mainly due to the high filling rate of the process and the low pressure which can be exerted via the melt due to the small bleed. However, this is needed to overcome the normally very low tendency to wetting between the metallic melt and the ceramic molding.
  • the preform must be heated significantly above the melt temperature in order to prevent premature solidification of the melt on the fiber body.
  • the method of stirring is primarily reserved for the particulate reinforcements, as the use of fibers can lead to a large increase in viscosity of the melt, which makes a homogeneous distribution of the fibers very difficult or even impossible.
  • the stirring result depends on the particle size used, the stirrer speed and the temperature. Insufficient choice of parameters can lead to clumping, flooding of the particles into the slag or their sedimentation on the crucible bottom. If the particles and the melt are reactive systems, reaction reactions at the interfaces may result due to the long contact time between the two phases, resulting in particle damage.
  • Example is the system magnesium - alumina, here is formed in the reaction between the two partners with decomposition of the particulate matter magnesium oxide and aluminum.
  • WO 03/027342 A From the WO 03/027342 A a method of the type mentioned is known. This process is based on a magnesium powder or a powder of a magnesium alloy and a silicon powder, which are processed to produce a more compact product. In this case, a heating and a reaction takes place between the magnesium and the silicon, so that a metal-matrix composite material containing Mg 2 Si as a reinforcing component is present. Furthermore, a hot forming process is provided.
  • the object of the present invention is to provide a method for the production of metal matrix composite materials of the type mentioned, which enables the production of light metal composite materials, in particular for use in temperature-loaded components, which is more variable and less expensive than the Hitherto known method and avoids the above-mentioned disadvantages associated with these.
  • the solution to this problem provides a method according to the invention for the production of metal matrix composite materials of the type mentioned above with the characterizing features of claim 1.
  • the production of the light metal composite material in the thixomolding process wherein in a metal matrix, an Mg 2 Si Phase with a volume content of at least 2%.
  • Mg-Mg 2 Si composites are to be prepared with a volume content of at least 2% Mg 2 Si by a granule of silicon or a silicon alloy and granules of magnesium or a magnesium alloy are supplied together to the thixomolding process and there under shear a form at least partially liquid melt, which solidifies in the form of a magnesium body.
  • Advantages of the method are the wide range of adjustable volume contents of Mg 2 Si, the ability to dispense with fiber or P siepreforms and determine the size and amount of Si particles, the amount and size of the forming Mg 2 Si crystals
  • properties such as thermal expansion coefficient, modulus of elasticity, tensile and yield strength, and wear behavior can be changed individually. So Si contents are adjustable, which can not be produced by melt metallurgy.
  • the thus cast material can be supplied to subsequent forming operations such as a forging process.
  • a cast body is produced from the metal-matrix composite material which is subsequently processed further.
  • the cast body is subsequently reshaped in at least one method step.
  • Such a forming process may include, for example, at least one forging process.
  • metal-matrix composites made by the process of this invention may be used to make pistons or other engine parts for diesel or gasoline fueled engines.
  • the metal-matrix composites are also suitable, for example, for the production of liners for shafts, cylinders and other rotationally symmetrical parts, especially in engines. They are also suitable for the production of other on wear stressed automotive parts such as brake discs.
  • the volume content of the Mg 2 Si phase in the metal matrix is preferably in the range between about 5 and about 40 volume percent.
  • the metal-matrix composites of the present invention are obtainable, for example, from standard alloys such as AZ91, AM50, MR1230D, MR1253M or other Mg die cast alloys obtained an addition of Si. Essential here is the reaction 2 Mg + Si ⁇ Mg 2 Si. In the context of the invention, an addition of at least about 2 percent by weight of Si and preferably at most about 15 percent by weight of Si is suitable.
  • the resulting volume percentages of Mg 2 Si are listed in Table 1 below, which represent exemplary levels of Mg 2 Si phase in the metal matrix composite.
  • Mg 2 Si is a comparatively high-melting phase with a melting point near 1100 ° C.
  • this phase is suitable as a reinforcement for improving the high-temperature properties of the matrix material.
  • This applies both to the creep behavior and characteristic values such as the thermal conductivity and also the thermal expansion coefficient. In addition to other physical and mechanical properties, these values can be adjusted specifically with regard to an application.
  • the exact numerical values depend, inter alia, on the base alloy, the volume fraction of Mg 2 Si, further precipitates in the matrix alloy, and also on the operating temperature or the operating temperature range. These data are to be determined experimentally for each application.
  • Mg 2 Si precipitates Another influencing factor is the manifestation of Mg 2 Si precipitates. Usually they are found as so-called "Chinese script" excretions, ie as acicular precipitates, which are very similar in their shape to Chinese characters. By the addition of alloying elements such. B. Ca, however, produce primary polygonal precipitates that behave like a particle reinforcement. Both types of precipitation also have an effect on mechanical and physical properties.
  • the parameters selected during further processing have a significant effect on the property profile. If a forming takes place, for example, by extrusion, then the alignment of planes of the Mg crystallites parallel to the extrusion direction leads to anisotropy.
  • the magnitude of the anisotropy depends on various factors, in particular on the forming ratio, the temperature in the tool, the preheating, heat transfer after pressing and thus the dynamic and static recrystallization.
  • the alloy composition including the influence of impurities is also an influencing factor.
  • the temperature control in the production of metal-matrix composite materials according to the inventive method is directly related to the selected alloy, the shot weight and the tool, in particular its component geometry, sprue, etc., the geometry of worm and cylinder in thixomolding, the feed rate and also the shooting speed. These parameters must be determined empirically for each component and are also dependent on the design of the machine and its data profile. Likewise, the properties also depend on the solid phase fraction. This affects the mechanical properties of the matrix alloy alone as well as the composite material, d. H. the combination of matrix and amplification.
  • the reaction means 2 Mg + Si ⁇ Mg 2 Si, that although the alloys build up a high proportion of liquid phase more quickly, at the same time there is an increasing proportion of solid phase due to the formation of Mg 2 Si.
  • the reaction not only takes place in the area of the cylindrical worm of the thixomolding machine, but can also take place after the casting in the workpiece. Especially in areas with accumulations of material, this behavior can be expected. Under certain circumstances, a reprint is therefore more successfully applied, as is still a part of matrix alloy in the molten phase by the exothermic reaction.
  • Related conclusions can be obtained by examining metallographic cuts.
  • the melting interval plays a major role.
  • the alloy AZ91 is listed, the melting interval in the range of 440 to 600 ° C. It is known from the literature that for this alloy a high proportion of liquid phase in the range of 95% leads to an improvement of the mechanical properties in the component. With such a liquid phase fraction, one can speak of a supercooled melt. After injection into the tool, a high nucleation rate is the result in the inventive method therefore at the same time a very high number of germs. This leads to the expression of a very fine structure, which has very good mechanical properties due to the Hall-Petsch relationship. Due to the supercooling of the melt, the shrinkage is also very low overall. It is the lower, the lower the proportion of liquid phase. This means at the same time that in comparison with die casting less internal stress and thus less distortion occurs.
  • the grain size of the granules is usually not a determinant size. Depending on the machine and selected component then each other a different screw geometry can be selected. The grain size and the grain shape must be matched to the screw geometry. This is completely independent of the alloy or the composite material. In the further consequence, the particle size ratio Mg-Si must be matched. However, this usually only makes sense for a previously defined screw geometry.
  • granules can, for example, by a simple conveyor at the same time or shortly after the granule application (both materials are still solid), which can be additionally attached to the machine.
  • a machine of conventional design can be used, as is available on the market, for example, from the companies Thixomat or Japan Steel Works.

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

Abstract

L'invention concerne un procédé permettant de produire des matériaux composites à base de matrice métallique, comprenant au moins une proportion de magnésium ou d'un alliage de magnésium, ainsi qu'au moins une étape de production, dans laquelle s'effectue un thixomoulage. Selon l'invention, une phase Mg2Si à teneur volumétrique d'au moins 2 % est intégrée dans une matrice métallique comprenant de préférence du magnésium ou un alliage de magnésium. Le procédé selon l'invention utilise la méthode du thixomoulage pour produire in situ un matériau composite métallique et présente l'avantage qu'il se produit une grande variation des teneurs volumétriques ajustables de la phase Mg2Si dans le matériau composite, ce qui permet d'effectuer des modifications individuelles du matériau composite. Ledit matériau composite à base de matrice métallique selon l'invention s'utilise notamment pour produire des éléments d'automobiles, sollicités en température, comme par exemple des pistons ou similaires.

Claims (9)

  1. Procédé de fabrication de matériaux composites à matrice métallique à base de Mg-Mg2Si, qui présentent une matrice métallique qui comprend du magnésium ou un alliage de magnésium et une phase de Mg2Si incorporée dans la matrice métallique,
    caractérisé en ce que partant d'un granulé de silicium ou d'un alliage de silicium et d'un granulé de magnésium ou d'un alliage de magnésium, on traite ces granulés ensemble dans une opération de thixomoulage et en ce qu'une phase de Mg2Si est incorporée à une teneur volumique d'au moins 2 % dans la matrice métallique.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on détermine la quantité ou la taille des cristaux de Mg2Si formés et/ou la teneur en silicium du matériau composite à partir de la taille et/ou de la quantité des particules de silicium ou d'alliage de silicium.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on prépare par l'opération du thixomoulage un corps moulé du matériau composite à matrice métallique et qu'on le traite encore ensuite.
  4. Procédé selon la revendication 3, caractérisé en ce que le corps moulé constitué du matériau composite à matrice métallique est ensuite façonné dans au moins une étape de traitement.
  5. Procédé selon la revendication 4, caractérisé en ce que le corps moulé en matériau composite à matrice métallique est ensuite façonné dans au moins une opération de forgeage et/ou une opération d'extrusion.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que lors de la fabrication du matériau composite, on effectue une addition d'au moins 2 pour cent en poids de Si et d'au plus 15 pour cent en poids de Si.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on incorpore dans la matrice métallique une phase de Mg2Si dans une proportion volumique d'au moins 5 % à au plus 40 %.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que lors de la fabrication du matériau composite à matrice métallique, on part d'un des alliages normalisés de magnésium AZ91, AM50, MRI230D, MRI253M ou d'un alliage de Mg pour moulage sous pression.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce qu'après addition de Si, la puissance de chauffage du dispositif de thixomoulage est diminuée dès que la fusion commence.
EP04765979A 2003-11-07 2004-10-16 Procede de production de materiaux composites a base de matrice metallique Expired - Fee Related EP1680246B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10352453A DE10352453A1 (de) 2003-11-07 2003-11-07 Verfahren zur Herstellung von Metall-Matrix-Verbundwerkstoffen
PCT/EP2004/011688 WO2005046911A1 (fr) 2003-11-07 2004-10-16 Procede de production de materiaux composites a base de matrice metallique

Publications (2)

Publication Number Publication Date
EP1680246A1 EP1680246A1 (fr) 2006-07-19
EP1680246B1 true EP1680246B1 (fr) 2007-07-11

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EP04765979A Expired - Fee Related EP1680246B1 (fr) 2003-11-07 2004-10-16 Procede de production de materiaux composites a base de matrice metallique

Country Status (7)

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US (1) US8282748B2 (fr)
EP (1) EP1680246B1 (fr)
JP (1) JP4444963B2 (fr)
KR (1) KR101110947B1 (fr)
CN (1) CN100402191C (fr)
DE (2) DE10352453A1 (fr)
WO (1) WO2005046911A1 (fr)

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US8715066B2 (en) 2010-06-14 2014-05-06 Automated Cash Systems, Llc System and method for electronic fund transfers for use with gaming systems
JP5137049B2 (ja) * 2011-04-08 2013-02-06 岡山県 マグネシウム合金チップ及びそれを用いた成形品の製造方法
CN103045891B (zh) * 2013-01-04 2015-03-11 南昌大学 一种原位Al2Y颗粒增强镁基复合材料的制备方法
US11508213B2 (en) * 2014-05-13 2022-11-22 Automated Cashless Systems, Inc. Enabling financial transactions for electronic gaming machines
US11410499B2 (en) * 2014-05-13 2022-08-09 Automated Cashless Systems, Inc. Financial gaming passport for cashless mobile gaming
CN104148608B (zh) * 2014-08-06 2018-08-03 南昌大学 一种基于超声制备半固态Mg2Si颗粒增强Mg-Al-Mn复合材料流变模型的建立方法
AT518825A1 (de) * 2016-05-31 2018-01-15 Lkr Leichtmetallkompetenzzentrum Ranshofen Gmbh Verfahren zur Herstellung eines Profils aus einer Metalllegierung
US11908277B2 (en) * 2021-05-24 2024-02-20 Automated Cashless Systems, Inc. Financial gaming passport for cashless mobile gaming

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Also Published As

Publication number Publication date
JP4444963B2 (ja) 2010-03-31
US8282748B2 (en) 2012-10-09
DE502004004318D1 (de) 2007-08-23
KR20070008518A (ko) 2007-01-17
KR101110947B1 (ko) 2012-02-20
DE10352453A1 (de) 2005-06-02
JP2007510545A (ja) 2007-04-26
CN1863626A (zh) 2006-11-15
CN100402191C (zh) 2008-07-16
US20070104606A1 (en) 2007-05-10
WO2005046911A1 (fr) 2005-05-26
EP1680246A1 (fr) 2006-07-19

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