EP1322439B1 - Compositions d'alliage metallique et procede d'obtention - Google Patents

Compositions d'alliage metallique et procede d'obtention Download PDF

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Publication number
EP1322439B1
EP1322439B1 EP01975249A EP01975249A EP1322439B1 EP 1322439 B1 EP1322439 B1 EP 1322439B1 EP 01975249 A EP01975249 A EP 01975249A EP 01975249 A EP01975249 A EP 01975249A EP 1322439 B1 EP1322439 B1 EP 1322439B1
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Prior art keywords
liquid
solid
composition
metal
agitation
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EP01975249A
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German (de)
English (en)
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EP1322439A4 (fr
EP1322439A1 (fr
Inventor
Merton C. Flemings
Raul A. Martinez-Ayers
Anacleto M. De Figueredo
James A. Yurko
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Massachusetts Institute of Technology
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Massachusetts Institute of Technology
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    • 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

Definitions

  • This invention relates to a method and apparatus for making metal compositions containing degenerate dendrites.
  • metal compositions Prior to the present invention, metal compositions have been made containing up to about 65 weight percent degenerate dendrites. Such compositions and their method of preparation are described in U.S. Patent Nos. 3,948,650, issued April 6, 1976 to Flemings et al and U.S. Patent 3,954,455, issued May 4, 1976 to Flemings et al.
  • a metal alloy is heated to form a liquid-solid mixture which is vigorously agitated to convert the dendrites derived from the alloy to degenerate dendrites.
  • the metal alloy is cooled while being vigorously agitated to the point where the viscosity of the high fraction solid material formed by cooling cannot be overcome by increasing shear forces on the high fraction solid material.
  • compositions can be cast directly or can be further solidified and subsequently reheated to form a thixotropic composition which can be cast directly (thixocasting).
  • thixocasting thixocasting
  • the solid degenerate dendrites formed by the present commercial practice of the process contain a large proportion of entrapped liquid formed from eutectic metal compositions. Furthermore, during the cooling cycle, some macrosegregation of solid and liquid occurs. The entrapped gas, entrapped eutectic metal compositions and solid liquid macrosegregation causes the overall metal alloy composition thus formed to be non-uniform with resultant non-uniform physical characteristics such as strength characteristics.
  • the thixocasting process wherein the high fraction solid material is completely solidified by cooling and then reheated to form a liquid-solid composition is effected in part in order to form more of a microstructure wherein the solid degenerate dendrites are spherodized, resulting in more uniform alloys.
  • the process is more costly since the solidified metal in the gates and runners of the forming apparatus must be reheated from the solid state to the liquid state resulting in the loss of the desired degenerate dendrite microstructure.
  • European Patent Application 96108499.3 discloses a process for forming a liquid-solid metal alloy composition which can be formed by casting.
  • a melt of the alloy is formed in one or more first vessels.
  • the melt then is transferred to an insulating vessel under cooling conditions wherein crystal nuclei form in the melt.
  • the melt then is further cooled in the insulating vessel under conditions to effect formation of spheroidal solids which form on the nuclei to produce the liquid-solid composition which is then cast.
  • the melt is transferred into the insulating vessel either by moving it over a cooled inclined jig which diverts a melt stream into the insulating vessel or by pouring a plurality of metal alloy melts into the insulating vessel.
  • one of the melts is at a temperature lower than the liquidus temperature of a second melt so that the crystal nuclei form in the second melt.
  • a major problem is that the poured melts entrap gas therein during the transfer and are retained therein due to the presence of solids. This results in a nonuniform final metal alloy composition having defects caused by the entrapped gas.
  • the cooling rate and degree of agitation are poorly controlled such that the crystal nuclei are limited in number and are not homogeneously dispersed in the liquid melt. This results in degenerate dendrites containing entrapped liquid and and in a formed metal alloy product having nonuniform physical characteristics throughout its volume.
  • a skin is formed on the bottom surface of the solidified product which then must be removed in order to obtain a desired homogeneous final metal alloy product.
  • European Patent Application No. 95 309498.4 (Publication NO. EPO 719606 A1) also discloses formation of a liquid-solid metal alloy composition by forming an alloy melt in a first vessel and transferring it to an insulating vessel over a cooled inclined surface to form crystal nuclei in the melt. The melt is then cooled to form a liquid-solid alloy composition containing spheroidal solids which can be cast. Since this process relies on a pouring step in the presence of solids, it also has the disadvantage of entrapping gas while forming spheroidal solids nonhomogeneously distributed in the final metal alloy product.
  • U.S. Patents 5,144,998; 5,555,926; 5,901,778 and 5,865,240 also disclose processes for forming a liquid-solid metal alloy composition which effects formation of a metal alloy melt in a first vessel which then is transferred to a second vessel under poorly controlled cooling and agitation conditions to form solid nuclei in the melt. Since the melt is transferred from one vessel to another while partially solidifying the melt, the problems associated with gas entrapment and nonhomogeneous sized spheroidal solids are encountered as set forth above.
  • EP 0 701 002 discloses a method of manufacturing metallic materials with fine grains in which molten material is agitated during cooling at a rate of ⁇ 1°C/second from ⁇ 30°C above liquidus such that the liquid content is adjusted to between 20-80% and the primary crystals are spheroidised.
  • a skinless homogeneous liquid-solid metal alloy compositions which are free from entrapped gas and wherein the solid component is free of an eutectic composition.
  • the primary solids have maximum sphericity which are homogeneously distributed throughout the volume of the metal alloy composition.
  • Such a metal alloy composition would be more easily shaped to provide a product having homogeneous physical characteristics throughout its volume.
  • a skinless homogeneous liquid-solid metal alloy composition can be formed from a molten metal alloy composition, free of entrapped gas, substantially free of entrapped eutectic in primary solids, and having primary solids which are substantially spherical by controlling conditions of cooling and vigorous agitation of a liquid precursor to the liquid-solid metal alloy. It has been found that rapid cooling and vigorous agitation can be effected for a short time over a narrow temperature range near the liquidus temperature of the molten metal alloy at a controlled cooling rate to form solid particle nuclei.
  • the resultant skinless composition comprises homogeneously sized primary spheroidal solid particles substantially free of eutectic metal alloy composition and which is free of entrapped gas.
  • the resultant liquid-solid metal alloy composition that can be formed such as by casting.
  • the present invention provides a process for forming a skinless metal alloy comprising primary solids substantially free of eutectic metal compositions, a secondary phase which is liquid or solid, primary solids having improved sphericity homogeneously distributed throughout the volume of the metal alloy which metal alloy is free of entrapped gas.
  • substantially free of entrapped eutectic metal compositions as used herein is meant less than about 2 % by volume, preferably less than 1 % by volume eutectic metal compositions entrapped in the primary solids based of the volume of primary solids.
  • the primary solids of the metal alloy compositions of this invention are characterized by an overall improved sphericity as compared to metal alloy composition of the prior art.
  • the process of this invention comprises a first step of forming a metal alloy liquid composition within a vessel.
  • the liquid metal alloy composition positioned within the vessel then can be cooled while vigorously agitating the cooled alloy such as by stirring under conditions to form solid nuclei particles while avoiding entrapment of gas within the agitated alloy compositions.
  • the liquid metal alloy composition can be transferred to a second vessel under conditions to prevent formation of solids prior to cooling.
  • the temperature of the walls of the second vessel can be above, at or below the liquidus temperature of the metal alloy composition. When the wall temperature is below the liquidus temperature, the wall temperature is raised to convert any formed solids to a liquid.
  • the liquid metal alloy composition is rendered quiescent so that entrapped gas, if any, floats to the liquid surface without interference by the presence of solids and is removed from the liquid.
  • the alloy is vigorously agitated while being cooled in a manner such that the solid nuclei are distributed throughout the metal liquid alloy composition substantially homogeneously.
  • the degree of agitation is such as to effect substantially homogeneous distribution of the formed crystal nuclei while avoiding entrapment of gas.
  • Agitation is effected while utilizing a rapid cooling rate range for a short time such as between about 1 second and about 1 minute, preferably between about 1 and about 30 seconds over a temperature range corresponding to a percent solidification of the alloy of between about 1 and about 20 % weight fraction solids, preferably between about 3 and about 7 % weight fraction solids while the liquid composition is cooled without agitation to effect forming the solid nuclei.
  • Agitation can be effected utilizing a cool probe in any manner which avoids excessive cavitation at the liquid surface thereby to avoid entrapment of gas in the liquid.
  • the probe can be rendered cool by passing a heat exchange fluid, such as water therethrough.
  • agitation means include one or a plurality of cylindrical rods provided with an internal cooling means, a helical probe, or the like that preferably extends the depth of the liquid.
  • the probe extends into a portion of the depth of the liquid up to substantially 100 % of the depth of the liquid to promote homogeneous dispersion of the crystal nuclei. Agitation then is ceased in a batch process or the liquid-solid alloy is removed from the source of agitation in a continuous process.
  • the resultant liquid-solid metal alloy composition then is cooled within the vessel to effect formation of spheroidal solid particles about the solid nuclei particles up to a concentration wherein the spheroidal solid particles increase the viscosity of the overall liquid-solid composition where it can be moved into a formation step such as a casting step.
  • the upper weight percent primary solids is between about 40 and about 65 percent and preferably contains 10 to 50 percent based on the total weight of the liquid solid composition.
  • the metal alloy composition comprising the primary solids and the secondary phase of the composition of this invention can be formed from a wide variety of metals or alloys which, when frozen from a liquid state without agitation form a dendritic network structure.
  • the composition of this invention includes primary solid discrete particles, the composition contains a secondary phase which can be either solid or liquid.
  • the secondary phase is solid when the metal composition is solid and liquid when the metal composition is partially liquid.
  • the secondary solid can be formed of one or more solid compositions.
  • the primary particles comprise small degenerate dendrites or nodules which are generally spheroidal in shape and are formed as a result of first agitating the melt while cooling when the secondary phase is liquid followed by cooling the secondary phase of the partially molten alloy under a quiescent condition without agitation.
  • the primary solid particles are made up of a single phase having an average composition different from the average composition of the surrounding secondary phase, which secondary phase can itself comprise primary and secondary phases upon further solidification.
  • primary solid as used herein is meant the phase or phases solidified to form discrete degenerate dendrite particles as the temperature of the melt is reduced below the liquidus temperature of the metal into the liquid-solid temperature range after the solid nuclei are formed and prior to casting the liquid-solid slurry form.
  • the primary solids are degenerate dendrites in that they are characterized by having smoother surfaces and less branched structures which approach a more spherical configuration than normal dendrites and do not have a dendrite structure when interconnection of the primary particles is effected to form a network dendritic structure.
  • the primary solids are substantially free on eutectics.
  • second solid as used herein is meant the phase or phases that solidify from the liquid existing in the slurry at a lower temperature than at which the primary solid particles are formed after formation of primary solids ceases.
  • Normally solidified alloys have branched dendrites separated from each other in the early stages of solidification, i.e., up to 15 to 20 wt. percent solid, and develop into an interconnected network as the temperature is reduced and the weight fraction solid increase.
  • the composition containing primary solids of this invention prevents formation of the interconnected network by maintaining the discrete primary particles separated from each other by the liquid phase even up to solid fractions of about 65 weight percent.
  • the secondary solid which is formed during solidification from the liquid phase subsequent to forming the primary solid contains one or more phases of the type which would be obtained during solidification by presently employed casting processes. That is, the secondary phase comprises solid solutions, or mixtures of dendrites, compounds and/or solid solutions.
  • the size of the primary particles depends upon the alloy or metal composition employed, the temperature of the solid-liquid mixture and the time the alloy spends in the solid-liquid temperature range.
  • the size of the primary particles depends on composition, thermo-mechanical history of the slurry, number of crystal nuclei formed, cooling rate and can range from about 1 to about 1,000 microns and are homogeneously sized throughout the metal alloy composition. It is preferred that the composition contain between 10 and 50 weight percent primary solids since these compositions have a viscosity which promotes ease of casting or forming.
  • compositions of this invention can be formed from any metal alloy system or pure metal regardless of its chemical composition which, when frozen from the liquid state without forming solid nuclei forms a dendritic structure. Even though pure metals and eutectics melt at a single temperature, they can be employed to form the composition of this invention since they can exist in liquid-solid equilibrium at the melting point by controlling the net heat input or output to the melt so that, at the melting point, the pure metal or eutectic contains sufficient heat to fuse only a portion of the metal or eutectic liquid. This occurs since complete removal of heat of fusion in a slurry employed in the casting process of this invention cannot be obtained by equating the thermal energy supplied and that removed by a cooler surrounding environment.
  • suitable alloys include lead alloys, magnesium alloys, zinc alloys, aluminum alloys, copper alloys, iron alloys, nickel alloys, cobalt alloys.
  • these alloys are lead-tin alloys, zinc-aluminum alloys, zinc-copper alloys, magnesium-aluminum alloys, magnesium-aluminum-zinc alloys, magnesium-zinc alloys, aluminum-silicon alloys, aluminum-copper-zinc-magnesium alloys, copper-tin bronzes, brass, aluminum bronzes, steels, cast irons, tool steels, stainless tells, super-alloys, and cobalt-chromium alloys, or pure metals such as iron, copper or aluminum.
  • A356 aluminum alloy stock were melted in a high-density graphite crucible 3 inches tall, with a 2.5 inch inner diameter, and a 0.25 inch wall thickness.
  • the crucible was placed inside an air-circulating resistance furnace, which was programmed to slowly cool the melt to a temperature 7 °C above its liquidus temperature. After holding at that temperature for several minutes, a solid copper rod with a 0.5 inch diameter, rotating at 1236 rpm, and initially at room temperature, was introduced in the furnace through an opening in its top and immersed into the melt 1.8 inches. The immersed, rotating rod provided a combination of rapid cooling and vigorous agitation of the melt.
  • FIG. 1(a) shows the three general processing steps of this invention.
  • step 1 the completely liquid melt 10 is formed prior to introducing rotating cold rod 12 into the melt 10.
  • step 2 crystal nuclei 14 are formed in the liquid melt 10 as a result of contact with the rotating cold rod 12.
  • step 3 the rod 12 is removed from the liquid-solid metal composition 16 in which spheroidal primary solids are formed while cooling is continued at a cooling rate shown in Fig. 1(b) until the composition is solid.
  • Figure 2(a) shows the homogeneous structure found throughout the volume of the solidified alloy after processing according to the above example and the cooling curve shown in Figure 2(b).
  • Figure 3(a) shows the same material after rapidly reheating to 590 °C, isothermally holding for approximately 10 minutes, and quenching according to the temperature profile of Figure 3(b).
  • Figure 4(a) and (b) shows the microstructure and temperature profile of reheated 3 inch diameter MHD billet (electromagnetically stirred) used commercially for thixocasting.
  • Figure 4(a) and (b) shows the microstructure and temperature profile for reheated 1 inch diameter of a commercially available a Stress Induced Melt Activation (SIMA) processed billet.
  • SIMA Stress Induced Melt Activation
  • A356 aluminum alloy stock were melted in a clay-graphite crucible 5 inches tall, with a 3 inch inner diameter, and a 0.6 inch wall thickness.
  • the crucible was placed inside an air-circulating resistance furnace, which was programmed to slowly cool the melt to a temperature slightly above its liquidus temperature.
  • a helix made with copper rod, rotating at 780 rpm, and initially at room temperature was introduced in the furnace through an opening in its top and immersed into the melt 2 inches.
  • the helix had a diameter of 1 inch and was made from rod with a 0.25 inch diameter.
  • the immersed, rotating helix provided a combination of rapid cooling and vigorous agitation of the melt.
  • FIG. 6(a) shows the homogeneous structure found throughout the volume of the solidified alloy after processing according to the above example and the cooling curve shown in Figure 6(b).
  • Figure 7(a) shows the same material after rapidly reheated to 590 °C, isothermally holding for approximately 10 minutes, and quenching according to the temperature profile in Figure 7(b).
  • A356 aluminum alloy stock were melted in a high-density graphite crucible 4 inches tall, with a 3 inch inner diameter, and a 0.5 inch wall thickness.
  • the crucible was placed inside an induction furnace, which was programmed to superheat the melt roughly 50 °C above its liquidus temperature. The furnace power was then shut off and the melt was allowed to slowly cool in the crucible.
  • a helix made with copper rod, rotating at 1000 rpm, and initially at room temperature was introduced in the furnace through an opening in its top and immersed into the melt 2 inches.
  • the helix has a diameter of 1 inch and was made from rod with a 0.25 inch diameter.
  • a vessel 20 comprises a first subvessel 22 for holding a completely liquid metal composition 24 which is introduced from vessel 26.
  • Subvessel 28 is adapted to receive water cooled rotating rod 30 and to receive the liquid metal composition through passageway 32 which can be opened or closed with conventional valve means (not shown). Crystal nuclei 34 are formed in subvessel 28 in the manner described above.
  • the liquid-solid composition 36 is removed from the agitating rod 30 in subvessel 28 either by gravity, under pressure or by a suitable pulling force on the composition 36 so that it can be cooled in the absence of agitation to form a composition that can be shaped either directly or by being solidified and then reheated to form a liquid-solid composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Claims (11)

  1. Procédé pour former une composition métallique sans croûte exempte de gaz piégé et ayant des dendrites dégénérées solides séparées distribuées homogènement dans une phase liquide de ladite composition métallique, lesdites dendrites dégénérées solides séparées étant sensiblement exemptes de matériaux eutectiques, qui comprend :
    (a) le chauffage d'une composition d'alliage métallique dans un récipient pour former un liquide exempt de substances solides et comprenant ladite composition métallique,
    (b) le refroidissement dudit liquide tout en agitant ledit liquide dans des conditions formant des noyaux solides dispersés homogènement dans ledit liquide tout en évitant le piégeage de gaz dans ledit liquide, à une vitesse de refroidissement comprise entre environ 2 °C par seconde et environ 10 °C par seconde pour former une composition liquide-solide contenant entre environ 1 et environ 10 fractions pondérales de solide,
    (c) l'arrêt de l'agitation dudit liquide ou l'enlèvement de l'alliage liquide-solide de la source d'agitation ; et
    (d) la poursuite du refroidissement dudit liquide pendant que ladite composition liquide-solide est au repos jusqu'à ce que ladite composition métallique soit solide.
  2. Procédé pour former une composition métallique sans croûte exempte de gaz piégé et ayant des dendrites dégénérées solides séparées distribuées homogènement dans une phase liquide de ladite composition métallique, lesdites dendrites dégénérées solides séparées étant sensiblement exemptes de matériaux eutectiques, qui comprend :
    (a) le chauffage d'une composition d'alliage métallique dans un récipient pour former un liquide exempt de substances solides et comprenant ladite composition métallique,
    (b) le refroidissement dudit liquide tout en agitant ledit liquide dans des conditions formant des noyaux solides dispersés homogènement dans ledit liquide tout en évitant le piégeage de gaz dans ledit liquide, à une vitesse de refroidissement comprise entre environ 2 °C par seconde et environ 10 °C par seconde pour former une composition liquide-solide contenant entre environ 1 et environ 10 fractions pondérales de solide,
    (c) l'arrêt de l'agitation dudit liquide ou l'enlèvement de l'alliage liquide-solide de la source d'agitation ;
    (d) la poursuite du refroidissement dudit liquide pendant que ladite composition liquide-solide est au repos jusqu'à ce que ladite composition métallique contienne jusqu'à environ 65 % en poids de substances solides primaires homogènement dispersées dans une phase secondaire liquide, et
    (e) le façonnage dudit mélange liquide-solide formé dans l'étape (d).
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel ledit liquide est refroidi dans ledit récipient.
  4. Procédé selon la revendication 1, dans lequel ledit liquide est transféré à un second récipient avant l'étape (b).
  5. Procédé selon la revendication 4, dans lequel les parois dudit second récipient sont initialement à une température supérieure à la température liquidus de ladite composition d'alliage métallique.
  6. Procédé selon la revendication 5, dans lequel les parois dudit second récipient sont initialement à la température de la température liquidus de ladite composition d'alliage métallique.
  7. Procédé selon la revendication 4, dans lequel les parois dudit second récipient sont initialement à une température inférieure à la température liquidus de ladite composition d'alliage métallique.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'agitation est effectuée avec une sonde s'étendant dans le liquide.
  9. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'agitation est effectuée avec plusieurs sondes s'étendant dans le liquide.
  10. Procédé selon la revendication 1, dans lequel lesdites étapes (b), (c) et (d) sont effectuées en continu.
  11. Procédé selon la revendication 2, dans lequel lesdites étapes (b), (c), (d) et (e) sont effectuées en continu.
EP01975249A 2000-09-21 2001-09-17 Compositions d'alliage metallique et procede d'obtention Expired - Lifetime EP1322439B1 (fr)

Applications Claiming Priority (3)

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US666700 1984-10-31
US66670000A 2000-09-21 2000-09-21
PCT/US2001/029223 WO2002024381A1 (fr) 2000-09-21 2001-09-17 Compositions d'alliage metallique et procede d'obtention

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EP1322439A1 EP1322439A1 (fr) 2003-07-02
EP1322439A4 EP1322439A4 (fr) 2004-09-15
EP1322439B1 true EP1322439B1 (fr) 2005-07-06

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EP (1) EP1322439B1 (fr)
JP (1) JP4667711B2 (fr)
AT (1) ATE299059T1 (fr)
AU (1) AU9458901A (fr)
CA (1) CA2422696C (fr)
DE (1) DE60111856T2 (fr)
ES (1) ES2245703T3 (fr)
WO (1) WO2002024381A1 (fr)

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US6918427B2 (en) * 2003-03-04 2005-07-19 Idraprince, Inc. Process and apparatus for preparing a metal alloy
US20050153082A1 (en) * 2004-01-14 2005-07-14 Holcombe Cressie E. Boron nitride reaction capsule/vessel
CN106413940B (zh) * 2014-05-16 2020-08-25 吉斯科有限公司 制造用于在低至零度的过热温度下铸造的熔融金属的方法
JP7247917B2 (ja) * 2020-02-19 2023-03-29 トヨタ自動車株式会社 半凝固溶湯の製造方法

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JP3920378B2 (ja) * 1996-07-24 2007-05-30 株式会社アーレスティ レオキャスト鋳造法及びレオキャスト鋳造装置
JPH1119759A (ja) * 1997-06-30 1999-01-26 Hitachi Metals Ltd ダイカスト鋳造方法および装置
JPH11197814A (ja) * 1998-01-20 1999-07-27 Honda Motor Co Ltd 半凝固金属の製造方法
EP1121214A4 (fr) * 1998-07-24 2005-04-13 Gibbs Die Casting Aluminum Procede et appareil de moulage semi-solide

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JP2004508939A (ja) 2004-03-25
EP1322439A4 (fr) 2004-09-15
JP4667711B2 (ja) 2011-04-13
CA2422696C (fr) 2009-03-17
ES2245703T3 (es) 2006-01-16
EP1322439A1 (fr) 2003-07-02
DE60111856T2 (de) 2006-05-11
ATE299059T1 (de) 2005-07-15
WO2002024381A1 (fr) 2002-03-28
CA2422696A1 (fr) 2002-03-28
DE60111856D1 (de) 2005-08-11
AU9458901A (en) 2002-04-02

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