EP1242641B1 - Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain - Google Patents

Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain Download PDF

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Publication number
EP1242641B1
EP1242641B1 EP00983193A EP00983193A EP1242641B1 EP 1242641 B1 EP1242641 B1 EP 1242641B1 EP 00983193 A EP00983193 A EP 00983193A EP 00983193 A EP00983193 A EP 00983193A EP 1242641 B1 EP1242641 B1 EP 1242641B1
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EP
European Patent Office
Prior art keywords
prealloy
melt
particles
al3ti
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.)
Expired - Lifetime
Application number
EP00983193A
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German (de)
English (en)
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EP1242641A1 (fr
Inventor
Walter Hotz
Heinrich Homberger
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3A Composites International AG
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Alcan Technology and Management Ltd
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Publication date
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Priority to EP00983193A priority Critical patent/EP1242641B1/fr
Publication of EP1242641A1 publication Critical patent/EP1242641A1/fr
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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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys

Definitions

  • the invention relates to a method for producing a grain refining agent according to the preamble of claim 1.
  • EP-A-0396389 describes a process for the continuous production of a Al-Ti-B grain refining alloy discloses, in which Ti and B-containing starting materials added to a molten aluminum reaction zone are, the melt being stirred in the reaction zone. A mixture the alloy formed becomes continuous together with the reaction products fed to a cleaning zone in which the slag with reaction products is collected on the surface of the melt and removed. The grain refining alloy formed is continuously removed from the cleaning station led to a casting station, in which the melt continuously is cast in one strand.
  • the cast strand can either directly have the desired strand or wire thickness, or it can be further Processing by rolling or extrusion to the desired grain refining material are processed.
  • the TiB 2 particles in the Al-Ti-B grain refining agents known today have a strong tendency to form agglomerates. This results in a reduced effect of the grain refining agent. Further disadvantages result from agglomerates and inclusions, which can lead to errors in the end product. Examples include gray lines, holes, material separations and stringers.
  • agglomerates occur preferentially on low-melting salts such as KF and NaCl as well as on oxide skins and can thereby further increase. As such, the agglomerates are "soft", can force themselves through filters and as such end up in a cast strand.
  • the invention is therefore based on the object of providing a process for producing an Al-Ti-B grain refining agent with which the formation of agglomerates of TiB 2 particles can be largely prevented and existing agglomerates can be deagglomerated.
  • cavitation ie the formation of bubbles
  • the implosion of which generates shock waves leads to the deagglomeration of agglomerated TiB 2 particles.
  • the latter methods include, for example, ultrasound treatment and vibration using a magnetostrictive resonator.
  • the grain refining agent produced by the process according to the invention brings about an improved and more homogeneous effect of the refining agent, particularly in the case of grain refinement of casting formats made of aluminum alloys, by a more homogeneous distribution of the individual TiB 2 particles, a better coating of the TiB 2 particles with Al 3 Ti phase and one Reduction or dispersion of any salts and oxide inclusions still present in the grain refining agent.
  • the master alloy is preferably set in motion before the liquidus temperature of the Al 3 Ti phase is undershot.
  • the effect of the grain refining agent produced according to the invention is shown by the fact that the individual, approximately 0.5 to 5 ⁇ m large TiB 2 particles have an excellent germination effect as a result of a coating formed from a thin Al 3 Ti layer and the particles are isolated and not as agglomerates act so that a comparable grain refinement can be achieved with a considerably smaller amount of grain refining agent than with grain refining agents according to the prior art.
  • the liquidus temperature of the Al 3 Ti phase is dropped below prematurely. This is especially the case when a master alloy with a high Ti content and a correspondingly higher liquidus temperature is produced or when a master alloy that has already solidified is assumed.
  • By heating the melt again above the liquidus temperature already precipitated Al 3 Ti particles can be completely dissolved again. This process typically takes 5 to 60 minutes, depending on the size of the Al 3 Ti particles.
  • the Ultrasonic movement of the melt with a frequency of 10 to 50 kHz generated.
  • the second cooling rate is preferably greater than 2 ° C./sec, in particular greater than 5 ° C / sec.
  • the master alloy melt can be cast into any format. However, preference is given to casting by vertical or horizontal continuous casting continuously produced strand. This strand can either already in the format of the rod or Cast wire material or in a further operation by rolling or presses to be processed into bar or wire material. Vertically cast, large-sized strands are mainly processed by extrusion. Horizontal continuous casting of formats is preferred relatively small diameter because this process is continuous Manufacturing allowed. The horizontally cast continuous casting formats are preferably by rolling to the desired bar or wire material processed.
  • a master alloy produced using the method according to the invention has a composition whose total titanium content exceeds the stoichiometric ratio of TiB 2 .
  • a preferred alloy used contains titanium and boron in a weight ratio of 5: 2 to 10: 1.
  • the process is suitable for producing master alloys with 0.15 to 20% by weight of titanium and 0.01 to 4% by weight of boron, it has proven to be advantageous if the master alloy contains 0.3 to 5, preferably 0.5 to 2,% by weight. % Ti and 0.02 to 1, preferably 0.05 to 0.5 wt .-% B contains.
  • the method according to the invention is particularly suitable for production of grain refining agents for the grain refining of aluminum and aluminum alloys.
  • FIG. 1 This is schematic in the Al-Ti equilibrium diagram shown in FIG. 1 Process flow shown for the production of an Al-Ti-B master alloy drawn in for grain refinement of aluminum alloys.
  • the illustration A of the alloy phases to the left of the 0.5% Ti line shows the processes during the preparation of an already solidified master alloy, the illustration B to the right of the 0.5% Ti line shows the processes during the solidification of the master alloy.
  • the master alloy melt contains TiB 2 particles in partially agglomerated form. Even before the liquidus temperature T L Al3Ti is undershot and shortly before the solidus temperature T s v of the pre-alloy of the Al 3 Ti phase is reached, the partially agglomerated TiB 2 particles are deagglomerated by a strong melt movement using ultrasound treatment at a frequency of, for example, 25 kHz and distributed homogeneously. Simultaneous controlled cooling with a first cooling rate v 1 of, for example, 0.5 ° C./sec, causes the deposition of a thin layer of the Al 3 Ti phase on the parallel surfaces of the TiB 2 particles and at the same time the formation of coarse-grained Al 3 Ti particles prevented.
  • a first cooling rate v 1 of, for example, 0.5 ° C./sec
  • a system 10 shown in FIG. 2 for producing an Al-Ti-B master alloy for grain refining of aluminum alloys comprises a reaction vessel 12 with an inlet channel 14 in its upper region and an outlet channel 16 in its lower region.
  • the reaction vessel 12 is surrounded by an induction motor 18 as an electromagnetic stirring device, with which the aluminum melt 20 located in the reaction vessel 12 is stirred vigorously to form a vortex 22.
  • Salts containing Ti and B, such as K 2 TiF 6 and KBF 4 are guided in the direction of arrow 24 into the vortex 22, which draws the salts into the aluminum melt 20.
  • the aluminum melt 20 with the reaction products is shown below through the outlet duct 16 via a further inlet duct 26 into the upper one Area of an aftertreatment boiler 28 out.
  • Another electromagnetic Stirring device 30 in the lower area of the aftertreatment boiler 28 leads to a lower turbulent zone 32 and an upper calm Zone 34.
  • the slag 36 formed by reaction products is over the removal opening 38 is removed from the aftertreatment boiler 28.
  • the cleaned aluminum melt 20 with the elements titanium and boron contained therein is fed as a pre-alloy in the lower region of the aftertreatment boiler 28 via a casting trough 38 to a mold, not shown in the drawing, of a horizontal continuous casting machine.
  • Two ultrasonic transmitters 40, 42 are arranged in the region of the casting trough 38, the sonotrodes 44, 46 of which immerse in the melt.
  • An induction heater 48 arranged below the casting trough 38 serves to heat the melt if its temperature should have already dropped below the liquidus temperature T L Al3Ti of the Al 3 Ti phase when the melt flows from the aftertreatment boiler 28 into the casting trough 38.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Procédé de fabrication d'un moyen d'affinage du grain sur la base d'un préalliage d'aluminium-titane-bore, qui consiste à introduire des matières de départ contenant Ti et B dans une masse d'aluminium fondue, ce qui provoque la formation de particules de TiB2, et à laisser durcir cette masse fondue de préalliage. Ledit préalliage est mis en mouvement, lorsqu'il se trouve entre la température liquidus (TLAl3Ti) de la phase Al3Ti et la température solidus (TSV) du préalliage, pendant une durée (Δt¿d?) suffisante pour que les particules de TiB2 se dispersent dans ledit préalliage, et simultanément refroidi à une première vitesse de refroidissement (v1), si bien que les particules de TiB2 agissent comme des germes pour la phase Al3Ti se formant au-dessous de la température liquidus (T?L¿Al3Ti) et que la surface des particules de TiB2 est au moins en partie couverte par une couche de Al3Ti. Ledit préalliage est ensuite refroidi au-dessous de la température solidus (TSV) à une deuxième vitesse de refroidissement (v2) plus élevée que la première vitesse de refroidissement (v1). Ledit procédé est particulièrement approprié pour la fabrication de moyens d'affinage de grain pour l'aluminium et les alliages d'aluminium.

Claims (12)

  1. Procédé pour produire un agent d'affinage de grain sur la base d'un alliage-mère d'aluminium-titane-bore par addition de matières de base contenant du titane et du bore dans une coulée d'aluminium avec formation de particules de TiB2, dans lequel les particules de TiB2 agissent comme des germes pour la phase Al3Ti se formant au-dessous de la température de liquidus (TL Al3Ti) de la phase Al3Ti et la surface des particules TiB2 sont recouvertes au moins en partie par un revêtement en Al3Ti, et solidification de cette coulée d'alliage-mère, caractérisé en ce que l'alliage-mère est mis en mouvement entre la température de liquidus (TL Al3Ti) de la phase Al3Ti et la température de solidus (Ts v) de l'alliage-mère pour disperser les particules de TiB2 dans la coulée afin de produire une cavitation par vibration à une fréquence de 50 Hz à 50 kHz, refroidi simultanément au-dessous de la température de solidus (Ts v) de l'alliage-mère à une première vitesse de refroidissement (v1) et ensuite à une vitesse de refroidissement (v2) supérieure à la première vitesse de refroidissement (v1) de plus de 1°C/sec.
  2. Procédé selon la revendication 1, caractérisé en ce que l'alliage-mère est mis en mouvement avant la descente au-dessous de la température de liquidus (TL Al3Ti) de la phase Al3Ti.
  3. Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce que, en cas d'une descente prématurée au-dessous de la température de liquidus (TL Al3Ti) ou d'une solidification déjà effectuée, l'alliage-mère est réchauffé au-dessus de la température de liquidus (TL Al3Ti) jusqu'à la dissolution complète de particules de AL3Ti déjà séparées dans la coulée.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le mouvement de la coulée est produit au moyen d'un résonateur magnétostrictif ou d'ultrasons.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la deuxième vitesse de refroidissement (v2) est supérieure à 2°C/sec, en particulier supérieure à 5°C/sec.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la coulée d'alliage-mère est coulée en une barre.
  7. Procédé selon la revendication 6, caractérisé en ce qu'une barre continue est produite, de préférence par coulée continue horizontale.
  8. Procédé selon la revendication 6 ou la revendication 7, caractérisé en ce que la barre est étirée en tiges ou en fil d'affinage de grain.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'alliage-mère présente une composition dont la teneur totale en titane dépasse le rapport stoechiométrique de TiB2.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'alliage-mère contient du titane et du bore dans le rapport de poids 5:2 à 10:1.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'alliage-mère contient 0,05 à 20, de préférence 0,1 à 5, en particulier 0,5 à 2 % en poids de titane et 0,01 à 4, de préférence 0,02 à 1, en particulier 0,05 à 0,5 % en poids de bore.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'on produit à partir de l'alliage-mère des agents d'affinage de grain pour l'affinage du grain d'aluminium et d'alliages d'aluminium.
EP00983193A 1999-12-10 2000-11-30 Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain Expired - Lifetime EP1242641B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00983193A EP1242641B1 (fr) 1999-12-10 2000-11-30 Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99811137 1999-12-10
EP99811137A EP1114875A1 (fr) 1999-12-10 1999-12-10 Procédé de production alliage d'mère aluminium-titanium-boron destiné à l'affinage du grain
EP00983193A EP1242641B1 (fr) 1999-12-10 2000-11-30 Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain
PCT/EP2000/012015 WO2001042521A1 (fr) 1999-12-10 2000-11-30 Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain

Publications (2)

Publication Number Publication Date
EP1242641A1 EP1242641A1 (fr) 2002-09-25
EP1242641B1 true EP1242641B1 (fr) 2004-02-18

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Application Number Title Priority Date Filing Date
EP99811137A Withdrawn EP1114875A1 (fr) 1999-12-10 1999-12-10 Procédé de production alliage d'mère aluminium-titanium-boron destiné à l'affinage du grain
EP00983193A Expired - Lifetime EP1242641B1 (fr) 1999-12-10 2000-11-30 Procede de fabrication d'un prealliage d'aluminium-titane-bore en tant que moyen d'affinage du grain

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP99811137A Withdrawn EP1114875A1 (fr) 1999-12-10 1999-12-10 Procédé de production alliage d'mère aluminium-titanium-boron destiné à l'affinage du grain

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US (1) US20030075020A1 (fr)
EP (2) EP1114875A1 (fr)
CA (1) CA2394485A1 (fr)
DE (1) DE50005366D1 (fr)
WO (1) WO2001042521A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR200504376A2 (tr) * 2005-11-02 2008-05-21 T�B�Tak-T�Rk�Ye B�L�Msel Ve Tekn�K Ara�Tirma Kurumu Tane küçültücü ön alaşım üretmek için bir proses
CN101768708B (zh) * 2010-02-05 2012-05-23 深圳市新星轻合金材料股份有限公司 通过控制压缩比来控制铝钛硼合金晶粒细化能力的变化量的方法
CN105671350A (zh) * 2015-03-19 2016-06-15 中信戴卡股份有限公司 一种铝合金细化剂、其制备方法及用途
EP3162460A1 (fr) 2015-11-02 2017-05-03 Mubea Performance Wheels GmbH Pièce coulée en alliage léger et procédé de sa fabrication
RU2625375C2 (ru) * 2015-12-03 2017-07-13 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Способ получения композиционных сплавов и установка для его осуществления
CN107377914A (zh) * 2017-08-04 2017-11-24 江西金世纪特种焊接材料有限公司 一种铝合金焊接材料熔炼连铸设备
FR3082763A1 (fr) 2018-06-25 2019-12-27 C-Tec Constellium Technology Center Procede de fabrication d une piece en alliage d aluminium
CN109371277A (zh) * 2018-12-11 2019-02-22 徐州宁铝业科技有限公司 一种用于铝合金熔炼的精炼剂及制备方法
CN110157935B (zh) * 2019-06-28 2021-05-07 上海大学 铸造铝硅合金用Al-V-B细化剂、其制备方法及应用
CN110195168B (zh) * 2019-07-12 2021-01-01 东北大学 一种铝-钛-硼细化剂板的制备工艺
CN114959348B (zh) * 2022-06-09 2023-12-05 上海大学 一种高分散度Al-xMB2细化剂的制备方法和应用方法
CN115558821B (zh) * 2022-12-06 2023-03-10 北京航空航天大学 一种实现TiB2尺寸可控的Al-Ti-B细化剂制备方法
CN115976373A (zh) * 2022-12-30 2023-04-18 中山瑞泰铝业有限公司 一种铝合金材料的加工工艺及其应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE349331B (fr) * 1970-04-28 1972-09-25 Svenska Aluminiumkompaniet Ab
US4612073A (en) * 1984-08-02 1986-09-16 Cabot Corporation Aluminum grain refiner containing duplex crystals
US5230754A (en) * 1991-03-04 1993-07-27 Kb Alloys, Inc. Aluminum master alloys containing strontium, boron, and silicon for grain refining and modifying aluminum alloys

Also Published As

Publication number Publication date
US20030075020A1 (en) 2003-04-24
EP1242641A1 (fr) 2002-09-25
CA2394485A1 (fr) 2001-06-14
WO2001042521A8 (fr) 2001-07-12
WO2001042521A1 (fr) 2001-06-14
EP1114875A1 (fr) 2001-07-11
DE50005366D1 (de) 2004-03-25

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