EP4244002B1 - Giessring zur herstellung eines produkts aus titanlegierung oder einer intermetallischen titan-aluminium-verbindung und verfahren mit verwendung davon - Google Patents

Giessring zur herstellung eines produkts aus titanlegierung oder einer intermetallischen titan-aluminium-verbindung und verfahren mit verwendung davon

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Publication number
EP4244002B1
EP4244002B1 EP21848163.8A EP21848163A EP4244002B1 EP 4244002 B1 EP4244002 B1 EP 4244002B1 EP 21848163 A EP21848163 A EP 21848163A EP 4244002 B1 EP4244002 B1 EP 4244002B1
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EP
European Patent Office
Prior art keywords
layer
alc
section
aln
alloy
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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.)
Active
Application number
EP21848163.8A
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English (en)
French (fr)
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EP4244002A1 (de
Inventor
Pierre Jean SALLOT
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.)
Safran SA
Original Assignee
Safran SA
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Application filed by Safran SA filed Critical Safran SA
Publication of EP4244002A1 publication Critical patent/EP4244002A1/de
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Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/06—Ingot moulds or their manufacture
    • B22D7/066—Manufacturing, repairing or reinforcing ingot moulds
    • B22D7/068—Manufacturing, repairing or reinforcing ingot moulds characterised by the materials used therefor
    • 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
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/041—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for vertical casting
    • 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
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • 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
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/055—Cooling the moulds
    • 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
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D15/00—Casting using a mould or core of which a part significant to the process is of high thermal conductivity, e.g. chill casting; Moulds or accessories specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045—Directionally solidified castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/06—Ingot moulds or their manufacture

Definitions

  • the present invention relates to the field of alloy production, in particular aeronautical alloys such as titanium-based alloys or TiAl intermetallics, in particular molding rings used to obtain ingots and processes using such molding rings.
  • the production of alloys mainly consists of heating a raw material in a crucible to melt it and pouring it into a molding ring which will give the ingot its shape.
  • Molding rings are generally made partly of copper and can be water-cooled. Copper is used because of its high thermal conductivity, which allows for good heat exchange, and also because of its good ductility, which facilitates its use by limiting the risk of breakage of this critical component. Therefore, copper is particularly suitable for manufacturing the areas of the molding ring that need to be cooled, known as cold zones.
  • foundry ceramics such as alumina, yttria, zirconia or their derivatives and composites, are generally the most suitable for the manufacture of alloys.
  • foundry ceramics are not thermally conductive, the use of an external electrical resistance is necessary. If induction heating is desired, an additional susceptor surrounding the molding ring is required to prevent direct coupling with the alloy being solidified within the molding ring. Indeed, such coupling generates circulating vortices of the molten alloy, thus destabilizing the solidification front.
  • Refractory metals are occasionally used to create hot zones.
  • the risk of chemical interactions between these metals and titanium-based or TiAl intermetallic alloys is high.
  • low-melting-point eutectics can form and lead to the development of critical defects in these alloys.
  • US2006070716 discloses a molding ring for continuous casting of a copper-based alloy, the ring made of an alloy in MAX phase.
  • This disclosure improves the situation.
  • such a molding ring Thanks to the use of such a molding ring, there is no risk of contamination of the manufactured alloy because the elements composing the molding ring material are elements generally present in titanium-based and TiAl intermetallic alloys. Therefore, there is no risk of the alloy being weakened by the inclusion of foreign elements, such as oxygen from foundry ceramics. Furthermore, such a molding ring exhibits good resistance to thermal shock and low thermal expansion.
  • the internal surface of the tube at the second section can be covered with one or more layers, each of the layers being in a material chosen from: Nb 4 Al 1 C 3 , Nb 2 AlC, Ti 2 AlC, Ti 2 AlN and AlN.
  • the first section and the second section can be connected to each other by a junction made by mechanical assembly or welding.
  • the molding ring may further include a third section extending from the second section to the second end, in particular over a length of at least 0.03 m, and made of a thermally conductive material.
  • the molding ring may further include a collar extending from the first end perpendicularly to the extension of the first section and outwards.
  • the present invention relates to a method of obtaining a titanium alloy or TiAl intermetallic product by plasma torch melting, the alloy having a directed structure.
  • the lines are isopleth lines joining points of the same angular value.
  • the solid line indicates the boundary between the region where the angle ⁇ is greater than 10° and the region where it is less than 10°. The darker the pattern, the larger the angle.
  • a molding ring according to the present invention is described below with reference to the figure 2 and to the figure 3 .
  • Such a molding ring 1 is particularly suitable for molding a titanium-based or TiAl intermetallic alloy ingot, formed from a tube with a first end 11 and a second end 12.
  • the molding ring 1 comprises a first section 13 and a second section 14 of tubing.
  • the first section 13 is made of copper and extends from the first end 11, in particular over a length L1 between 0.065 and 0.09 m .
  • the second section 14 is made of a MAX phase alloy and extends from the first section 13, in particular over a length L2 between 0.17 and 0.3 m; the MAX phase being selected from: Nb4Al1C3, Nb2AlC , Ti2AlC , and Ti2AlN . These MAX phases are the most compatible with the compositions of titanium-based alloys and TiAl intermetallic alloys.
  • such alloys include other elements, the most commonly used being zirconium, molybdenum, niobium, chromium, tungsten, vanadium, carbon, and boron.
  • the only MAX phases considered all have aluminum at the A site.
  • these selected MAX phases are compatible with the melting temperatures of titanium-based alloys and TiAl intermetallic alloys, which are close to 1500°C.
  • the molding ring 1 may further include a third section 15 extending from the second section 14 to the second end 12, in particular over a length L3 of at least 0.03 m, and made of a thermally conductive material.
  • the lengths L1, L2, and L3 were determined by simulation, notably to obtain a solidification front perpendicular to the pulling direction, i.e., to the longitudinal axis of the molding ring 1.
  • the results of these simulations are shown in the... figures 3 to 6
  • These figures show the impact of the choice of lengths L1 and L2 on the flatness of the solidification front at different drawing speeds, respectively 0.00015 m/s, 0.0003 m/s, and 0.00045 m/s.
  • the flatter the solidification front the clearer the corresponding region. It can be seen that the higher the drawing speed, the smaller the region corresponding to a solidification front forming an angle of less than 10° with a plane perpendicular to the drawing direction.
  • the angle is measured at the inner surface of the mold ring in a plane that includes the longitudinal axis of the drawn ingot, collinear with the drawing direction; this angle is that between a straight line resulting from the intersection of the plane in question and the plane perpendicular to the drawing axis, and a straight line tangent to the curve resulting from the intersection of the plane in question and the solidification front measured at the inner surface of the mold ring.
  • the length ranges were defined to achieve a good compromise between the flatness of the solidification front and the range of drawing speeds over which the process is applicable. When lengths L1 and L2 are located within the aforementioned ranges, the angle is less than 10° for a wide range of drawing speeds.
  • the first section 13 is a cold zone and serves, in particular, as a heat exchange surface between the alloy poured into the molding ring and a heat transfer fluid circuit, allowing the alloy temperature to be maintained at approximately 25°C at this point. Copper exhibits high thermal conductivity while also being ductile.
  • the second section 14 is a hot zone, that is to say a zone which is heated to remelt the alloy at this level, thus allowing a solidification front to be obtained as flat as possible, in particular with an angle of less than 10°.
  • the Nb4AlC3 and Nb2AlC phases can be used alone.
  • the layer orders presented above are important. Indeed, they prevent the formation of secondary phases at the interfaces between the different layers; the existence of a continuous solid solution is essential between these phases.
  • Configurations featuring AlN in the innermost layer are particularly suited to drawing aluminum-free alloys with melting temperatures above 1600°C.
  • the layers preferably have a thickness between 50 ⁇ m and 1000 ⁇ m. For example: 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 250 ⁇ m, 500 ⁇ m, or 750 ⁇ m.
  • the choice of materials mentioned above also has the advantage of facilitating the manufacturing of the molding ring. Indeed, all these materials are now available in powder form.
  • the various powders chosen can be densified or deposited as layers.
  • the temperatures required to densify these different materials are relatively similar, between 1400 and 1700°C, which allows, in particular, for their co-sintering.
  • the following method can be implemented: the different materials are positioned concentrically in a mold that allows for high-temperature sintering of the powders. If thin layers are required (i.e., less than 250 ⁇ m), the cold spray process can be used to create the necessary layers on the inner surface of the molding ring.
  • the magnetron sputtering process in high-power pulse regime can be implemented on the inner face of the molding ring.
  • An additional layer not in contact with the molten alloy, can be added to the mold ring, for example, on the outer surface, but generally at any level, with the sole limitation being that it does not come into contact with the molten alloy.
  • This additional layer is made of a ferromagnetic material, particularly a ferromagnetic alloy. This additional layer promotes magnetic coupling with the mold ring. Examples of materials for such a layer include pure iron, FeCo or FeSi alloys, etc.
  • the additional layer preferably has a thickness of at least 250 ⁇ m, for example, 300 ⁇ m, 350 ⁇ m, 400 ⁇ m, 450 ⁇ m, or 500 ⁇ m. This additional layer can be obtained by thermal spraying or cold spraying.
  • the first section 13 and the second section 14 can be connected to each other by a junction 17 made by mechanical assembly or welding.
  • the junction 17 is preferably located in the cold zone of the molding ring. This avoids limiting the assembly techniques and also allows the ductility of copper to be taken advantage of, thus reducing bending stresses in the layer stacks in the MAX phase.
  • the third section 15, when planned, is a cold zone for cooling the alloy.
  • the second end 12 of the molding ring may have a chamfer facilitating the insertion of the molding ring into the installation for producing alloy ingots by drawing.
  • the chamfer may be formed in the third section 15, in particular so as to completely occupy the third section 15.
  • the molding ring 1 may further include a collar 16 extending from the first end 11 perpendicularly to the extension of the first section 13 and outwards.
  • the collar 16 is preferably circular, but not necessarily so. It may be square, rectangular, or triangular, optionally with rounded corners.
  • the inner wall of the molding ring is a mathematical cylinder, that is, a surface generated by parallel generatrices around a closed curve and extending between the first and second ends 11, 12.
  • the closed curve is a circle (the drawn ingot is therefore a right cylinder with a circular base)
  • the present invention is not limited to such a shape.
  • the closed curve can be a square, a rectangle, or a triangle. The corners can also be rounded.
  • the wall thicknesses at the first section 13, the second section 14 , and the third section 15 are preferably chosen according to the maximum temperature gradient that the molding ring 1 must withstand between its inner surface in contact with the alloy and its outer surface. Specifically, the thicknesses are chosen according to Math. 1 and Math. 2 above.
  • the thickness e1 of the first section L1 is less than the thickness e2 of the section L2.
  • a shoulder is formed between the first and second sections. This shoulder is preferably greater than 90° and preferably corresponds to the junction of the materials of the two sections.
  • the molding ring 1 described above can be advantageously used in a process for obtaining a titanium alloy or TiAl intermetallic product by plasma torch melting to obtain an alloy with a directed structure.
  • the process may further include cooling the third section 15 of the molding ring forming a second cold zone, in particular by a second cooling means 6.
  • the process may include the supply of raw material MP (in particular in the form of scrap, briquettes, bars, a sponge/master alloy mixture, etc.), the heating of the raw material MP (for example by plasma torch 8, by electric arcs, by induction, by electron bombardment, etc.) melting the raw material MP into a crude molten alloy, the refining of the crude molten alloy (including for example the stabilization of the temperature of the alloy and the removal of impurities), and the pouring 2 of the refined molten alloy into the molding ring 1.
  • the heating of the raw material MP for example by plasma torch 8, by electric arcs, by induction, by electron bombardment, etc.
  • the refining of the crude molten alloy including for example the stabilization of the temperature of the alloy and the removal of impurities

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Continuous Casting (AREA)
  • Forging (AREA)
  • Powder Metallurgy (AREA)
  • Arc Welding In General (AREA)

Claims (8)

  1. Gießring zum Gießen eines Barrens aus einer Legierung auf Titanbasis oder einer TiAl-Intermetalllegierung, der aus einem Rohr mit einem ersten und einem zweiten Ende gebildet ist und umfasst:
    - einen ersten Abschnitt aus Kupfer, der sich von dem ersten Ende aus erstreckt;
    - einen zweiten Abschnitt aus einem Material aus einer Legierung mit MAX-Phase, der sich von dem ersten Abschnitt aus erstreckt;
    wobei die MAX-Phase ausgewählt ist aus: Nb4Al1C3, Nb2AlC, Ti2AlC und Ti2AlN.
  2. Gießring nach Anspruch 1,
    wobei die Innenfläche des Rohrs am zweiten Abschnitt mit einer oder mehreren Schichten beschichtet ist, wobei jede der Schichten aus einem Material besteht, das ausgewählt ist aus: Nb4Al1C3, Nb2AlC, Ti2AlC, Ti2AlN und AIN.
  3. Gießring nach Anspruch 2, wobei
    dann, wenn das Material Nb4Al1C3 ist, die Innenfläche des Rohrs am zweiten Abschnitt von außen nach innen beschichtet ist mit:
    - einer einzigen Schicht aus Nb2AlC;
    - einer ersten Schicht aus Nb2AlC und einer zweiten Schicht aus Ti2AlC;
    - einer ersten Schicht aus Nb2AlC, einer zweiten Schicht aus Ti2AlC und einer dritten Schicht aus AIN; oder
    - einer ersten Schicht aus Nb2AlC, einer zweiten Schicht aus Ti2AlC, einer dritten Schicht aus Ti2AlN und einer vierten Schicht aus AIN;
    dann, wenn das Material Nb2AlC ist, die Innenfläche des Rohrs am zweiten Abschnitt von außen nach innen beschichtet ist mit:
    - einer einzigen Schicht aus Ti2AlC;
    - einer ersten Schicht aus Ti2AlC und einer zweiten Schicht aus AIN; oder
    - einer ersten Schicht aus Ti2AlC, einer zweiten Schicht aus Ti2AlN und einer dritten Schicht aus AIN;
    dann, wenn das Material Ti2AlC ist, die Innenfläche des Rohrs am zweiten Abschnitt von außen nach innen beschichtet ist mit:
    - einer einzigen Schicht aus AIN; oder
    - mit einer ersten Schicht aus Ti2AlN und einer zweiten Schicht aus AIN.
  4. Gießring nach einem der Ansprüche 1 bis 3,
    wobei das Rohr ferner eine weitere Schicht aus einem ferromagnetischen Material umfasst.
  5. Gießring nach einem der Ansprüche 1 bis 4,
    wobei der erste Abschnitt und der zweite Abschnitt durch eine Verbindung miteinander verbunden sind, die durch mechanisches Fügen oder Schweißen hergestellt ist.
  6. Gießring nach einem der Ansprüche 1 bis 5,
    ferner umfassend einen dritten Abschnitt, der sich vom zweiten Abschnitt bis zum zweiten Ende erstreckt, insbesondere über eine Länge von mindestens 0,03 m, und aus einem wärmeleitenden Material besteht.
  7. Gießring nach einem der Ansprüche 1 bis 6,
    ferner umfassend einen Kragen, der sich senkrecht zur Erstreckung des ersten Abschnitts vom ersten Ende nach außen erstreckt.
  8. Verfahren zur Herstellung eines Erzeugnisses aus Titanlegierung oder TiAl-Intermetalllegierung durch Aufschmelzen mittels Plasmabrenners, wobei die Legierung eine gerichtete Struktur aufweist, wobei das Verfahren umfasst:
    - Auswählen eines Gießrings nach einem der vorhergehenden Ansprüche, bei dem die Länge L1 des ersten Abschnitts zwischen 0,065 und 0,09 m und die Länge L2 des zweiten Abschnitts zwischen 0,17 und 0,3 m liegt, und bei dem die Dicke e1 und e2 des ersten bzw. zweiten Abschnitts so gewählt ist, dass R exp L 1 min Δ T 1 A 1 − 1 ≤ e 1 ≤ R exp L 1 max Δ T 1 A 1 − 1 R exp L 2 min Δ T 2 A 2 − 1 ≤ e 2 ≤ R exp L 2 max Δ T 2 A 2 − 1 wobei R der Innenradius des Gießrings ist, ΔT1 der gewünschte maximale Temperaturgradient im ersten Abschnitt ist, ΔT2 der gewünschte maximale Temperaturgradient im zweiten Abschnitt ist, A1 gleich 9°C.m und A2 gleich 60 °C.m ist, L1min gleich 0,065 m ist, L1max gleich 0,09 m ist, L2min gleich 0,17 m ist und L2max gleich 0,3 m ist,
    - Erhitzen der Oberfläche der geschmolzenen Legierung am Gießring;
    - Abkühlen des ersten Abschnitts des Gießrings, der einen Kaltbereich bildet, wobei durch das Abkühlen ein halbfester Legierungsring entsteht;
    - Erhitzen des zweiten Abschnitts des Gießrings, der einen Heißbereich bildet, wodurch eine Erstarrungsfront der Legierung in diesem Heißbereich erzeugt wird, deren Ebenheit in Bezug auf eine Ebene senkrecht zu einer Abzugsrichtung weniger als 10° beträgt; und
    - Abziehen der erstarrten Legierung mit einer Geschwindigkeit von mehr als 10-4 m/s entlang einer Abzugsrichtung.
EP21848163.8A 2020-12-03 2021-12-02 Giessring zur herstellung eines produkts aus titanlegierung oder einer intermetallischen titan-aluminium-verbindung und verfahren mit verwendung davon Active EP4244002B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2012626A FR3117051B1 (fr) 2020-12-03 2020-12-03 Anneau mouleur d’obtention d’un produit en alliage de titane ou en intermétallique TiAl et procédé l’utilisant
PCT/FR2021/052183 WO2022117965A1 (fr) 2020-12-03 2021-12-02 Anneau mouleur pour l'obtention d'un produit en alliage de titane ou en intermetallique tial et procede l'utilisant

Publications (2)

Publication Number Publication Date
EP4244002A1 EP4244002A1 (de) 2023-09-20
EP4244002B1 true EP4244002B1 (de) 2025-11-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP21848163.8A Active EP4244002B1 (de) 2020-12-03 2021-12-02 Giessring zur herstellung eines produkts aus titanlegierung oder einer intermetallischen titan-aluminium-verbindung und verfahren mit verwendung davon

Country Status (5)

Country Link
US (1) US12042849B2 (de)
EP (1) EP4244002B1 (de)
CN (1) CN116806176A (de)
FR (1) FR3117051B1 (de)
WO (1) WO2022117965A1 (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2595596B1 (fr) * 1986-03-13 1988-04-29 Cegedur Lingotiere permettant de regler le niveau suivant lequel elle est en contact avec la surface libre du metal dans une coulee verticale
JPH0352747A (ja) * 1989-07-17 1991-03-06 Kobe Steel Ltd 高融点且つ活性な金属の連続鋳造方法
DE19747305A1 (de) * 1997-10-25 1999-04-29 Km Europa Metal Ag Kokille für eine Stranggießanlage
US20060070716A1 (en) * 2004-10-04 2006-04-06 Russel Nippert Method and system for continuously casting copper alloys
US7926548B2 (en) * 2004-11-16 2011-04-19 Rti International Metals, Inc. Method and apparatus for sealing an ingot at initial startup
CN201385110Y (zh) * 2009-05-02 2010-01-20 大连理工大学 一种金属水平连续铸造的复合式铸型装置
CN103056340B (zh) * 2013-01-06 2015-05-20 沈阳化工大学 用TiAlC基陶瓷粉料作为金属及钛合金铸造面层的方法

Also Published As

Publication number Publication date
FR3117051A1 (fr) 2022-06-10
US12042849B2 (en) 2024-07-23
US20230415224A1 (en) 2023-12-28
FR3117051B1 (fr) 2023-04-28
WO2022117965A1 (fr) 2022-06-09
CN116806176A (zh) 2023-09-26
EP4244002A1 (de) 2023-09-20

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