WO1994012676A1 - Alliage mere aluminium-antimoine - Google Patents

Alliage mere aluminium-antimoine Download PDF

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Publication number
WO1994012676A1
WO1994012676A1 PCT/NL1993/000247 NL9300247W WO9412676A1 WO 1994012676 A1 WO1994012676 A1 WO 1994012676A1 NL 9300247 W NL9300247 W NL 9300247W WO 9412676 A1 WO9412676 A1 WO 9412676A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminium
antimony
master alloy
atomization
process according
Prior art date
Application number
PCT/NL1993/000247
Other languages
English (en)
Inventor
Edward Hendrik Klein Nagelvoort
Jan Pieter Mulder
Petrus Cornelis Van Wiggen
Original Assignee
Kbm-Metaalindustrie B.V.
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 Kbm-Metaalindustrie B.V. filed Critical Kbm-Metaalindustrie B.V.
Priority to AU57188/94A priority Critical patent/AU5718894A/en
Publication of WO1994012676A1 publication Critical patent/WO1994012676A1/fr

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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
    • C22C21/04—Modified aluminium-silicon alloys
    • 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
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys

Definitions

  • the invention relates to an aluminium-antimony master alloy, to a process for the preparation of aluminium-antimony master alloys and to the use of these master alloys as structure refiner during the solidification of molten aluminium-silicon alloys.
  • structure refiner is used for a compound or composition which, after addition and mixing and/or dissolution in a molten metal or alloy, either as such or as a newly formed compound, induces during solidification the formation of smaller crystals than would have been the case when the structure refiner would not have been used.
  • antimony has been used as a structure refiner for the aforesaid aluminium-silicon alloys, especially eutectic or hypo-eutectic aluminium-silicon alloys, i.e. alloys containing up to about 12 % by weight of silicium, see for example the article by . Meyer, "Vertician der Einfl ⁇ sse von Strontium, Antimon oder Natrium auf das Aluminium- Silizium-Eute ti um in Abhangmaschine von der Abk ⁇ hlungs- embod", Aluminium, 50 1967, 11, pages 699- 703.
  • hypo-eutectic aluminium- silicon alloys first primary aluminium crystals are formed until the eutectic composition is obtained, whereafter simultaneously aluminium crystals together with silicon crystals are formed.
  • the silicon crystals show an acicular form and are fairly large when no structure refiner is used. When a structure refiner is used these silicon crystals are relatively small and show a fibrous character, resulting in the above described improved properties.
  • the aluminium-antimony master alloy was supplied to the bath of molten metal or molten alloy in the form of ingots.
  • substantial amounts of dross are formed during solution of the ingots and the long stay of the aluminium bath before and during casting.
  • aluminium-antimony master alloy to a bath of molten aluminium-silicon in an efficient and safe way.
  • aluminium-antimony master alloys containing a relatively large amount of antimony may be obtained by atomization of molten alloy. Preferably atomization is followed by consolidation of the obtained solid particles, for instance by extrusion.
  • the master alloys thus obtained dissolve very rapidly in liquid aluminium and are very suitable for use as effective structure refiners of eutectic and hypo-eutectic aluminium-silicon alloys. Due to their high ductility (elongation > 5-10 %) in line (addition in the launder) feeding using conventional coil feeders is possible.
  • the present invention therefore relates to a process for the preparation of an aluminium-antimony master alloy suitable for use as structure refiner during the solidification of molten aluminium-silicon alloys, comprising atomization of a molten alloy containing 3 to 30 % by weight of antimony and a balance of aluminium and quick cooling of the atomized droplets to obtain solid particles.
  • atomization is followed by consolidation of the obtained solid particles.
  • the present invention relates to an aluminium-antimony master alloy suitable for use as structure refiner during solidification of molten aluminium-silicon alloys, the master alloy at least comprising 3 to 30 %w of antimony and a balance of aluminium, the antimony being comprising in antimony-aluminide intermetallic particles, said particles having a particle size up to 25 ⁇ m and an average particle size in the range from 1 to 15 ⁇ m and distributed homogeneously in the master alloy.
  • the master alloy obtained by the above described process are very efficient structure refiners for aluminium- silicon alloys, especially eutectic and hypo-eutectic alloys.
  • the amount of antimony taken up in the casting alloy is extremely high, and is usually between 95 and 100 %. Under normal circumstances there is no gas pick up during the addition, while also dross formation is very small or even absent.
  • the master alloys are effective for low as well as high cooling rates in the aluminium-silicon alloys in which they should be active.
  • the dissolution velocity is high (usually less than two minutes) .
  • the temperature loss is relatively low when compared with conventionally cast aluminium-antimony master alloys which contain less antimony.
  • the alloy obtained is very ductile, the alloy may be produced in the form of wire or coils, thus making it possible to feed the alloy using conventional coil feeders.
  • the amount of antimony is preferably between 5 and
  • certain amounts of one or more other elements may be present in the master alloy.
  • iron, silicon and copper, either alone or in combination may be present in the master alloy up to a total amount of 15 %w, which elements promote dissolution of the master alloy in the bath.
  • small amounts of titanium, or the combination of titanium and boron, titanium in the range from 0.1 to 2 %w and boron in the range from 0.02 to 0.4 %w may be added to the master alloy in order to further improve the structure refiner effect. Also trace amounts of the usual impurities may be present.
  • the atomization of the molten alloy may be carried out by methods known in the art.
  • the atomization process may be described as any comminution process of liquid metal streams in which a molten metal stream is disintegrated into small droplets, usually spherical, oval, elliptical, rounded cylindrical etc. droplets, particles or ligaments.
  • gas atomization The break up of a liquid stream brought about by the improvement of high-pressure jets of gas is usually called "gas atomization”.
  • the use of centrifugal force to break up a liquid stream is known as “centrifugal atomization”.
  • Atomization in vacuum is known as “vacuum atomization”.
  • the use of ultrasonic energy to effect break up is referred to as “ultrasonic atomization”.
  • a very suitable atomization process which can be used in the process of the present invention is gas atomization.
  • a stream of liquid alloy passes a nozzle where it is atomized into small droplets which droplets are cooled during their following flight through the so called atomization chamber.
  • a suitable atomization gas is air. Also nitrogen and argon may be used.
  • a typical metal flow rate varies between 5 and 60 kg/min, especially between 10 and 45 kg/min.
  • a typical gas flow rate varies between 2 and 12 m /min, especially between 4 and 8 m 3 /min.
  • the gas pressure is suitably chosen between 500 and 5000 kPa.
  • the temperature of the molten alloy is suitably chosen from the melting point of the alloy to a temperature 50 to 250°C above the melting point, especially 100 to 150°C.
  • the atomized droplets are cooled and solidified during their flight through the atomization chamber.
  • This chamber may be purged with an inert gas.
  • the powder may be collected as dry particles or cooled with water at the bottom of the chamber.
  • the atomization chamber is usually fairly large, for instance at least 6 to 10 meters, in order to ensure complete solidification of the powder particles before they reach the bottom of the collection chamber.
  • the atomization process may be carried out vertically (upwardly or downwardly) or horizontally.
  • the cooling rate in the above described gas atomization processes is suitably between 50 and 10 4 °C/s, preferably between 100 and 10 °C/s, which is much faster than cooling rates obtained in conventional casting processes (0.001-10°C/s) , e.g. in the case of direct chill casting.
  • a preferred atomization process for the process of the present invention is centrifugal atomization.
  • a stream of molten metal is impinged on a rapidly spinning disk or cup in the top of an atomization chamber.
  • the liquid metal is mechanically atomized and thrown off the disk or cup.
  • the rotating disk or cup may be equipped with vanes or holes through which the molten alloy exits.
  • the rotating body may be made from e.g. a metal or a ceramic material.
  • a typical metal flow rate varies between 4 and 60 kg/min, especially between 8 and 45 kg/min.
  • the temperature of the molten alloy is suitably chosen from the melting point of the alloy to a temperature 50 to 250°C above the melting point, especially 100 to 150°C.
  • the atomized droplets are cooled and solidified during their flight through the atomization chamber.
  • the height of the atomization chamber is usually fairly large, for instance 6 to 10 meters, in order to ensure complete solidification of the powder particles before they reach the bottom.
  • the diameter of the obtained particles will usually be between 50 and 5000 micrometer, and is preferably between 100 and 4000 micrometer.
  • the cooling rate in this process is suitably between 50 and 10 4 °C/s, preferably between 100 and 10 4 °C/s.
  • the consolidation of the obtained powders may be carried out using conventional, mechanical techniques. In this respect reference is made to the Metals Handbook, 9th edition, especially Volume 7, Consolidation of Metal Powders, page 293 ff.
  • a coherent metal structure is obtained. Net shaped articles may be produced, but usually billets, rod, rod pieces, strip, wire and tubing products are made.
  • a preferred consolidation technique is extrusion in which the metal particles are forced through an orifice or die of the appropriate shape. Cold extrusion is usually suitable, although hot extrusion also may be used.
  • the master alloy can be fed to the alloy bath in unconsolidated form.
  • the master alloy containing certain amounts of elements as mentioned above, the master alloy for example obtained by said atomization process, comprises intermetallic antimony-aluminide particles having a particle size up to 25 ⁇ m and an average particle size in the range from 1 tot 15 ⁇ m. Said intermetallic particles contain antimony and aluminium in substantially the same amounts and are distributed homogeneously in the master alloy.
  • homogeneous distribution is to be understood as having no clustered antimony-aluminide particles.
  • the amount of master alloy to be added to the cast alloy is usually chosen in such a way that the desired degree of structure refining is obtained.
  • the actual amount may be determined in each case by make up of the particular aluminium-silicon alloy to be treated, the cooling rate and the degree of structure refinement desired.
  • the master alloy is added to the molten aluminium-silicon alloy in an amount which introduces at least 0.002 % (w/w) antimony in the alloy, and preferably between 0.01 and 0.30 % (w/w), more preferably between 0.02 and 0.20 % (w/w).
  • the use of the before mentioned master alloys is especially suitable in the case of eutectic and hypo eutectic aluminium-silicon alloys.
  • the amount of silicon in such alloys varies between 3 and 12 %, especially between 6 and 11 %.
  • some minor amounts of other elements may be present in the alloy, for instance iron (up to 3 %) , copper (up to 6 %) , manganese (up to 1 %) , magnesium (up to 2 %) , nickel (up to 3 %) , chromium (up to 1 %) , zinc (up to 3 %) and tin (up to 1 %) .
  • trace amounts of the usual impurities may be present.
  • the invention further relates to the master alloys which are obtained by the above described processes and to the use of these master alloys in the structure refining during the solidification of aluminium-silicon cast alloys.
  • the invention also relates to a process for the structure refining during the solidification of aluminium-silicon alloys, especially eutectic and hypo eutectic aluminium-silicon alloys, and to aluminium-silicon alloys thus prepared, as well as to products made from these alloys.

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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 Metal Powder And Suspensions Thereof (AREA)

Abstract

Procédé de préparation d'un alliage mère aluminium-antimoine servant de raffineur de structure dans la solidification d'alliages aluminium-silicium en fusion. Le procédé consiste à atomiser un alliage en fusion renfermant de 3 à 30 % en poids au moins d'antimoine, le solde étant de l'aluminium, et à refroidir rapidement les gouttelettes atomisées afin d'obtenir des particules solides. Par la suite, la consolidation des particules solides ainsi obtenues peut se produire. L'antimoine se présente sous la forme de particules d'aluminiure d'antimoine présentant une grosseur allant jusqu'à 25 νm et une grosseur moyenne comprise entre 1 et 15 νm, et étant réparties de manière homogène dans l'alliage mère.
PCT/NL1993/000247 1992-11-24 1993-11-23 Alliage mere aluminium-antimoine WO1994012676A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57188/94A AU5718894A (en) 1992-11-24 1993-11-23 Aluminium-antimony master alloy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92203630.6 1992-11-24
EP92203630 1992-11-24

Publications (1)

Publication Number Publication Date
WO1994012676A1 true WO1994012676A1 (fr) 1994-06-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1993/000247 WO1994012676A1 (fr) 1992-11-24 1993-11-23 Alliage mere aluminium-antimoine

Country Status (2)

Country Link
AU (1) AU5718894A (fr)
WO (1) WO1994012676A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107190162A (zh) * 2017-05-18 2017-09-22 大连理工大学 铝硅合金细化变质一体化处理中间合金及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1588346A (fr) * 1968-02-12 1970-04-10
US3797084A (en) * 1972-12-18 1974-03-19 Gould Inc Method of making a fine dispersion aluminum base bearing
US4069369A (en) * 1970-12-15 1978-01-17 Gould Inc. Fine dispersion aluminum base bearing
JPS63192837A (ja) * 1987-02-05 1988-08-10 Nissan Motor Co Ltd アルミニウム系軸受合金
EP0398449A1 (fr) * 1989-05-19 1990-11-22 KBM-Metaalindustrie B.V. Alliage mère aluminium-strontium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1588346A (fr) * 1968-02-12 1970-04-10
US4069369A (en) * 1970-12-15 1978-01-17 Gould Inc. Fine dispersion aluminum base bearing
US3797084A (en) * 1972-12-18 1974-03-19 Gould Inc Method of making a fine dispersion aluminum base bearing
JPS63192837A (ja) * 1987-02-05 1988-08-10 Nissan Motor Co Ltd アルミニウム系軸受合金
EP0398449A1 (fr) * 1989-05-19 1990-11-22 KBM-Metaalindustrie B.V. Alliage mère aluminium-strontium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 12, no. 472 (C - 551) 9 December 1988 (1988-12-09) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107190162A (zh) * 2017-05-18 2017-09-22 大连理工大学 铝硅合金细化变质一体化处理中间合金及其制备方法

Also Published As

Publication number Publication date
AU5718894A (en) 1994-06-22

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