EP0360104B1 - Verfahren und Vorrichtungen zum Erzeugen von Drähten aus amorphen Metallegierungen - Google Patents

Verfahren und Vorrichtungen zum Erzeugen von Drähten aus amorphen Metallegierungen Download PDF

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Publication number
EP0360104B1
EP0360104B1 EP89116705A EP89116705A EP0360104B1 EP 0360104 B1 EP0360104 B1 EP 0360104B1 EP 89116705 A EP89116705 A EP 89116705A EP 89116705 A EP89116705 A EP 89116705A EP 0360104 B1 EP0360104 B1 EP 0360104B1
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EP
European Patent Office
Prior art keywords
jet
gas
alloy
nozzle
cooling liquid
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
EP89116705A
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English (en)
French (fr)
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EP0360104A1 (de
Inventor
Denis Bijaoui
Gérard Duchefdelaville
Guy Jarrige
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.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Compagnie Generale des Etablissements Michelin SCA
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Publication date
Application filed by Compagnie Generale des Etablissements Michelin SCA filed Critical Compagnie Generale des Etablissements Michelin SCA
Priority to AT89116705T priority Critical patent/ATE92805T1/de
Publication of EP0360104A1 publication Critical patent/EP0360104A1/de
Application granted granted Critical
Publication of EP0360104B1 publication Critical patent/EP0360104B1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/01—Continuous casting of metals, i.e. casting in indefinite lengths without moulds, e.g. on molten surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars

Definitions

  • the invention relates to wires of amorphous metal alloys and in particular the methods and devices making it possible to obtain wires of amorphous metal alloys by rapid cooling in a liquid medium, these alloys being in particular based on iron.
  • the projected jet tends to resolve in drops, which causes either a discontinuity of the jet leading to the impossibility of having a continuous wire, or to the formation of a continuous wire whose section is irregular.
  • the patent US-A-3 845 805 describes a fixed system for producing metallic filaments by casting a jet in a cooling liquid which is circulated by passing it through a tube.
  • the jet passes through a gas which can possibly promote the formation of a stabilizing skin on the jet.
  • the thickness of this gas is very small, of the order of 0.2 cm.
  • the object of the invention is to remedy these drawbacks, by proposing the method according to claim 1 and the device according to claim 7, the preambles of these claims being based on the aforementioned US-A-4,523,626 patent.
  • the amorphous threads obtained with the process or the device according to the invention can be used, for example, to reinforce plastic or rubber articles, in particular tire casings.
  • FIG. 3 is a side view and Figure 4 is a section taken along a plane passing through the axis of rotation xx ′ and by the point of contact 0 of the jet 7 with the layer 8, this section being shown schematically by the segments in a straight line IV-IV in FIG. 3.
  • a part of the installation 21 is shown in detail in FIG. 5, this FIG. 5 being a section made along a plane passing through the axis yy ′ of the installation 21, the section of FIG. 5 being shown diagrammatically by the straight line segments VV in FIG. 4.
  • the installation 21 is arranged outside the drum 11.
  • This installation 21 comprises a reservoir 22 constituted by a ceramic crucible, for example made of zircon or alumina.
  • the crucible 22 rests on the insulating spacer 23 made for example of aluminous refractory concrete.
  • Around the crucible 22 is arranged a cylindrical jacket 24 made for example of zircon.
  • a stuffing 25 in the form of compacted powder of alumina.
  • the jacket 24 is surrounded by the induction coil 26 capable of melting the amorphizable alloy 4 based on iron by passage of electric current.
  • the assembly of the crucible 22, the spacer 23, the jacket 24 and the packing 25 is surrounded by an enclosure 27 comprising two walls 28, 29, made of steel, a coolant 30, for example water, being disposed between these walls 28, 29.
  • a part 31, in the form of an inverted cup, is disposed in the opening 32 passing through the bottom 33 of the crucible 22 and the bottom 34 of the enclosure 27.
  • the spacer 23 and the jacket 24 rest directly on the bottom 34 of the enclosure 27.
  • the cup 31 is made for example of zircon.
  • the top 35 of the cup 31 is crossed by a nozzle 36, made for example of zirconia or alumina, the part 31 therefore serving as a support for the nozzle 36.
  • the opening 37 of this nozzle 36 is disposed along the axis yy ′ which is the axis of the opening 32 and the axis of the installation 21.
  • the installation 21 also comprises a device 38 comprising the flange 39 which makes it possible to apply this device against the enclosure 27.
  • the device 38 also comprises the cylindrical enclosure 40, and the annular rim 41 on which is applied a part 42 in the form of an inverted cup, the top 43 of which has an opening 44 situated under the opening 37 of the nozzle 36 and having the axis yy ′.
  • the flange 39, the cylinder 40 and the flange 41 are made for example of steel and the part 42 is made of ceramic, for example of zircon.
  • the internal volume 45 of the cylinder 40, under the rim 41, and the internal volume 46 of the cup 42 communicate with each other through the opening 47 and together constitute the enclosure 48.
  • the seal at the flange 39 is ensured by an O-ring 49, for example made of rubber.
  • the operation of the device 20 is as follows: The passage of electric current through the induction coil 26 allows the amorphizable alloy 4 placed in the crucible 22 to be melted. This molten alloy 4 allows the upper part of a steel ferrule 50 previously disposed around the support to be melted 31 between this support 31 on the one hand and the crucible 22, the enclosure 27 and the spacer 23 on the other hand. This partial melting of the ferrule 50 forms the steel seal 51 between the support 31 and the crucible 22. This seal 51 combined with the O-ring 49 ensures good sealing of the installation 21.
  • the argon 5 under pressure, placed in the crucible 22 above the alloy 4 allows the extrusion of this alloy, through the nozzle 36, in the form of a jet 7 which passes through the opening 44 of the part 42 along the axis yy ′ and crosses the interior volumes 46 and 45, that is to say the enclosure 48 to finally leave the installation 21 and reach the layer 8 of water 9 where it solidifies very quickly to give the wire 12.
  • the speed quenching is, in known manner, of the order of 105 ° C / second, the water 9 being cooled by a known refrigeration system arranged around the drum 11, this system not being shown in the drawing for the purpose of simplification.
  • a small amount of hydrogen 52 is made to arrive through the opening 53 made in the cylinder 40 above the rim 41.
  • the hydrogen 52 thus fills the space 54 which is outside the cup 42 between it ci and the support 31, the cylinder 40 and the rim 41.
  • the hydrogen 52 is thus thus in contact with the nozzle 36.
  • the jet 7 In order for the jet 7 to be able to undergo very rapid quenching in the layer 8 so as to obtain an amorphous wire 12, it is essential that the jet 7 remains liquid throughout the entire length L, that is to say that the jet 7 must be at a temperature higher than the melting temperature of the alloy 4 during the impact of the jet 7 with water 9.
  • the hydrogen 52 and the oxidizing gas mixture 55 must therefore not significantly cool the jet 7, the solidification being carried out only within the layer 8.
  • the alloy 4 contains silicon and the stabilization of the jet 7 is carried out by oxidation of the silicon, the silicon content in the alloy being greater than 0.2% ( % atomic).
  • the jet 7 flows for example from top to bottom, as in the device 20 described above, in a vertical direction, and the axis xx 'of the drum 11, and therefore the generatrices of the water cylinder 80 limiting the layer 8 in the direction of the axis xx ', make an angle of 40 to 70 ° with the vertical.
  • the jet 7 it is possible to envisage causing the jet 7 to flow in other directions, at the outlet of the installation 21, for example horizontally or from bottom to top.
  • the jet 7 is continuous throughout its journey from the nozzle 36 to the layer 8, without the formation of drops.
  • This combined with the very rapid cooling achieved thanks to the layer 8, makes it possible to obtain an amorphous wire 12 whose circular section with a diameter of 160 ⁇ m has a regular shape over its length.
  • the crucible 22 has been shown as a tank in which the alloy 4 is fused, but one could use a tank supplied with alloy 4 previously melted, this supply being for example continuous.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Wire Processing (AREA)
  • Coating With Molten Metal (AREA)
  • Metal Extraction Processes (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Ropes Or Cables (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Soft Magnetic Materials (AREA)

Claims (12)

  1. Verfahren zur Herstellung eines Drahts (12) aus einer amorphen Metallegierung durch Erzeugung eines Strahls (7) einer amorphisierbaren geschmolzenen Legierung (4) durch eine Düse (36) und Einleitung des Strahls (7) in eine Kühlflüssigkeit (9), die durch Zentrifugalkraft gegen die Innenwand (10) einer rotierenden Trommel (11) angelegt wird, in der Weise, daß eine rasche Verfestigung des Strahls (7) erzielt wird, der dann den Draht (12) aus amorphem Metall ergibt,
    gekennzeichnet durch folgende Merkmale:
    a) Es wird eine Legierung (4) verwendet, die mehr als 0,2 % Silicium, ausgedrückt in Atom-%, enthält;
    b) der Strahl (7) wird mit einer Einrichtung (21) erzeugt, die einen Behälter (22) für die Legierung (4) und ein Gas (5) unter Druck umfaßt, das auf die geschmolzene Legierung vor der Düse einwirkt und gegenüber der Legierung inert ist;
    c) bevor der Strahl (7) die Kühlflüssigkeit (9) erreicht, wird er mit einem Gas (55) in Kontakt gebracht, das zu einer Oxidation des Siliciums des Strahls (7) befähigt ist, wobei diese Oxidationsreaktion an der Oberfläche in der Weise erfolgt, daß sich eine Schicht um den Strahl (7) herum bildet, die ihn stabilisieren kann;
    d) der vom Strahl (7) zwischen der Düse (36) und der Kühlflüssigkeit (9) zurückgelegte Weg liegt zwischen 10 und 100 cm.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gas (55), das zu einer Oxidation des Siliciums des Strahls befähigt ist, ein Gasgemisch ist, das Wasserstoff oder ein inertes Gas und mindestens ein weiteres Gas enthält, das unter Wasserdampf, Kohlendioxid und Kohlenmonoxid ausgewählt ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Strahl (7) so erzeugt wird, daß das gegenüber der Legierung inerte Gas (5) vor der Düse (36) auf die geschmolzene Legierung (4) einwirken gelassen wird, wobei der Druck des Gases (5) mindestens 5 bar und die Geschwindigkeit des Strahls mindestens 10 m/s betragen.
  4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Strahl (7) so erzeugt wird, daß das gegenüber der Legierung inerte Gas (5) vor der Düse (36) auf die geschmolzene Legierung (4) einwirken gelassen wird, wobei der Druck des Gases (5) unter 3,5 bar und die Geschwindigkeit des Strahls unter 8 m/s betragen.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Düse (36) auf der Seite des Strahls (7) mit einem nichtoxidierenden Gas (52) in Kontakt gebracht wird, bevor der Strahl (7) mit dem oxidierenden Gas (55) in Kontakt kommt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Einrichtung (21) zur Erzeugung des Strahls (7) außerhalb der Trommel (11) vorgesehen ist.
  7. Vorrichtung (20) zur Herstellung eines Drahts (12) aus einer amorphen Metallegierung, die aufweist:
    einen Behälter (22) zur Aufnahme einer amorphisierbaren, Silicium enthaltenden Legierung (4) in flüssigem Zustand, eine Düse (36),
    Mittel (5) zum Aufbringen von Druck, um die flüssige Legierung (4) in Form eines Strahls (7) durch die Düse (36) hindurch in Richtung einer Kühlflüssigkeit (9) strömen zu lassen, die eine rasche Verfestigung des Strahls (7) erlaubt, der dann den Draht (12) aus amorphem Metall ergibt, sowie
    eine rotierende Trommel (11), welche die Ausbildung einer Schicht (8) der Kühlflüssigkeit (9) ermöglicht, die durch Zentrifugalkraft gegen die Innenwand (10) der Trommel (11) angelegt wird und in die der Strahl (7) eingeleitet wird,
    gekennzeichnet durch folgende Merkmale:
    a) Der Behälter (22) ist außerhalb der Trommel (11) angeordnet;
    b) die Vorrichtung (20) weist einen Behälter (48) auf, der sich zwischen dem Behälter (22) und der Kühlflüssigkeit (9) befindet, wobei der Strahl (7) durch diesen Behälter (48) hindurchgeht, bevor er zur Kühlflüssigkeit (9) gelangt, und der Behälter (48) zur Aufnahme eines Gases (55) ausgebildet ist, welches das Silicium des Strahls (7) oxidieren kann, wobei diese Oxidationsreaktion an der Oberfläche in der Weise erfolgt, daß sich um den Strahl (7) herum eine Schicht bildet, die ihn stabilisieren kann;
    c) die Düse (36) und der Behälter (48) sind derart angeordnet, daß der vom Strahl (7) zwischen der Düse (36) und der Kühlflüssigkeit (9) zurückgelegte Weg zwischen 10 und 100 cm liegt.
  8. Vorrichtung (20) nach Anspruch 7, dadurch gekennzeichnet, daß das Gas (55) ein Gasgemisch ist, das Wasserstoff oder ein Inertgas und mindestens ein weiteres Gas enthält, das unter Wasserdampf, Kohlendioxid und Kohlenmonoxid ausgewählt ist.
  9. Vorrichtung (20) nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß der Behälter (22) ein gegenüber der Legierung (4) inertes Gas (5) enthält, dessen Druck mindestens 5 bar beträgt, wobei dieses Gas unter Druck die Erzielung einer Geschwindigkeit des Strahls (7) von mindestens 10 m/s erlaubt.
  10. Vorrichtung (20) nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß der Behälter (22) ein gegenüber der Legierung (4) inertes Gas (5) enthält, dessen Druck unter 3,5 bar beträgt, wobei dieses Gas unter Druck die Erzielung einer Geschwindigkeit des Strahls (7) von unter 8 m/s erlaubt.
  11. Vorrichtung (20) nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß sie Mittel (53) aufweist, die es erlauben, ein nichtoxidierendes Gas (52) mit der Düse (36) auf der Seite des Strahls (7) vor dem Behälter (48) in Kontakt zu bringen.
  12. Vorrichtung (20) nach einem der Ansprüche 7 bis 11, dadurch gekennzeichnet, daß die Einrichtung (21) zur Erzeugung des Strahls (7) außerhalb der Trommel (11) angeordnet ist.
EP89116705A 1988-09-21 1989-09-09 Verfahren und Vorrichtungen zum Erzeugen von Drähten aus amorphen Metallegierungen Expired - Lifetime EP0360104B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89116705T ATE92805T1 (de) 1988-09-21 1989-09-09 Verfahren und vorrichtungen zum erzeugen von draehten aus amorphen metallegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8812423A FR2636552B1 (fr) 1988-09-21 1988-09-21 Procedes et dispositifs pour obtenir des fils en alliages metalliques amorphes
FR8812423 1988-09-21

Publications (2)

Publication Number Publication Date
EP0360104A1 EP0360104A1 (de) 1990-03-28
EP0360104B1 true EP0360104B1 (de) 1993-08-11

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EP89116705A Expired - Lifetime EP0360104B1 (de) 1988-09-21 1989-09-09 Verfahren und Vorrichtungen zum Erzeugen von Drähten aus amorphen Metallegierungen

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Country Link
US (1) US5000251A (de)
EP (1) EP0360104B1 (de)
JP (1) JPH02117752A (de)
KR (1) KR0125762B1 (de)
CN (1) CN1036570C (de)
AT (1) ATE92805T1 (de)
AU (1) AU616305B2 (de)
BR (1) BR8904774A (de)
CA (1) CA1336125C (de)
DE (1) DE68908310T2 (de)
ES (1) ES2042916T3 (de)
FR (1) FR2636552B1 (de)
OA (1) OA09092A (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2672522A1 (fr) * 1991-02-08 1992-08-14 Michelin & Cie Procede et dispositif pour obtenir en continu un fil par extrusion dans un liquide.
FR2673551B1 (fr) * 1991-03-05 1993-06-11 Siderurgie Fse Inst Rech Procede et dispositif de coulee continue de fil metallique de faible diametre directement a partir de metal liquide.
FR2676946A1 (fr) * 1991-05-27 1992-12-04 Michelin & Cie Procede et dispositif pour obtenir un fil en alliage metallique amorphe a base de fer.
CN1073479C (zh) * 1996-05-09 2001-10-24 冶金工业部包头稀土研究院 晶态和非晶态稀土金属合金细丝及其生产方法和装置
KR20020000965A (ko) * 2000-06-23 2002-01-09 신영주 안전밸브
US7077186B2 (en) * 2003-12-11 2006-07-18 Novelis Inc. Horizontal continuous casting of metals
US7589266B2 (en) * 2006-08-21 2009-09-15 Zuli Holdings, Ltd. Musical instrument string
CN101532117B (zh) * 2008-03-12 2010-12-15 中国科学院金属研究所 一种连续金属玻璃纤维的制备方法
FR2956410B1 (fr) * 2010-02-16 2012-01-27 Snecma Dispositif pour l'obtention de fibres ceramiques enduites par voie liquide d'une gaine metallique epaisse
KR102800631B1 (ko) * 2023-04-27 2025-04-29 (주)씨큐파이버 유리냉각을 통한 고융점 합금 비정질 와이어의 제조 방법 및 장치

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3845805A (en) * 1972-11-14 1974-11-05 Allied Chem Liquid quenching of free jet spun metal filaments
FR2367563A1 (fr) * 1976-10-15 1978-05-12 Michelin & Cie Procede et installation
FR2367562A1 (fr) * 1976-10-15 1978-05-12 Michelin & Cie Perfectionnements a la fabrication de fil metallique par coulee continue dans un fluide refroidisseur
US4339255A (en) * 1980-09-09 1982-07-13 Energy Conversion Devices, Inc. Method and apparatus for making a modified amorphous glass material
EP0039169B1 (de) * 1980-04-17 1985-12-27 Tsuyoshi Masumoto Amorphe Metallfasern und dazugehöriges Herstellungsverfahren
JPS58173059A (ja) * 1982-03-03 1983-10-11 Unitika Ltd 金属細線の製造方法
JPS60247445A (ja) * 1984-05-21 1985-12-07 Unitika Ltd 金属細線の連続製造方法及び装置

Also Published As

Publication number Publication date
EP0360104A1 (de) 1990-03-28
CA1336125C (fr) 1995-07-04
US5000251A (en) 1991-03-19
BR8904774A (pt) 1990-05-01
FR2636552A1 (fr) 1990-03-23
CN1041302A (zh) 1990-04-18
CN1036570C (zh) 1997-12-03
JPH02117752A (ja) 1990-05-02
KR0125762B1 (ko) 1997-12-26
KR900004435A (ko) 1990-04-12
FR2636552B1 (fr) 1990-11-02
AU616305B2 (en) 1991-10-24
AU4153389A (en) 1990-03-29
ATE92805T1 (de) 1993-08-15
DE68908310D1 (de) 1993-09-16
DE68908310T2 (de) 1993-12-16
OA09092A (fr) 1991-10-31
ES2042916T3 (es) 1993-12-16

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