EP0530968A1 - Méthode pour la coulée par solidification directionnelle de l'aluminure de titane - Google Patents

Méthode pour la coulée par solidification directionnelle de l'aluminure de titane Download PDF

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Publication number
EP0530968A1
EP0530968A1 EP92306862A EP92306862A EP0530968A1 EP 0530968 A1 EP0530968 A1 EP 0530968A1 EP 92306862 A EP92306862 A EP 92306862A EP 92306862 A EP92306862 A EP 92306862A EP 0530968 A1 EP0530968 A1 EP 0530968A1
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EP
European Patent Office
Prior art keywords
melt
chill
casting
titanium aluminide
comprised
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.)
Withdrawn
Application number
EP92306862A
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German (de)
English (en)
Inventor
Shyh-Chin Huang
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General Electric Co
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General Electric Co
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Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0530968A1 publication Critical patent/EP0530968A1/fr
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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
    • 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
    • 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

Definitions

  • This invention is related to a method for directional solidification casting of a titanium aluminide alloy.
  • the primary dendrites are aligned, as are the grain boundaries.
  • An effective way to control heat flow is in a mold assembly having thin refractory sidewalls and a metal chill, usually water cooled, at the lower end of the mold.
  • the sidewalls of the mold assembly are heated above the liquidus temperature of the alloy by a mold heating device such as an induction heater. Molten metal is poured into the mold, and after a pause of a few minutes to allow the grains to nucleate and begin to grow on the chill, the mold is withdrawn at a controlled rate from the mold heating device.
  • a mold heating device such as an induction heater. Molten metal is poured into the mold, and after a pause of a few minutes to allow the grains to nucleate and begin to grow on the chill, the mold is withdrawn at a controlled rate from the mold heating device.
  • some reaction between molten metal and mold occurs from titanium reduction of the ceramic oxides.
  • An oxygen-rich surface is formed on the casting that stabilizes the alpha phase in titanium forming a distinct "alpha case" layer on the cast surface.
  • the brittle alpha case layer can be removed by chemical milling. Diffusion of reaction products into the surface of the casting is dependent on the time the titanium is at a temperature sufficient to react with the mold. The depth of surface contamination must be taken into consideration in the initial wax pattern tool design. Hence, the wax pattern and casting are made slightly oversized, and final dimensions are achieved through careful chemical milling. Metal superheat, mold temperature and thermal conductivity, and rapid removal of heat after casting are other factors in to control for producing a satisfactory casting.
  • face coatings and refractory materials that have been developed for casting titanium and titanium alloys are given in U.S. Patent 4,740,246. Briefly described, some of the face coating compositions are; a silica binder prepared either from ethyl silicate, aqueous colloidal silica or the like, is used to bond boron oxide; a zirconia refractory bonded by zirconium acetate; a stabilized zirconia refractory bonded by colloidal silica, and a zirconia sol binder for a refractory material selected from fused yttrium oxide, a fused mixture of yttrium oxide and zirconium oxide, a fused blend of zirconium oxide and yttrium oxide with an oxide of rare earth elements of the periodic table elements with an atomic number of 57-71, a fused blend of zirconium oxide with an oxide of the same rare earth elements, and a fused blend of yttrium oxide
  • the difficulty in providing mold materials or face coatings having minimized reaction with molten titanium is further exacerbated for forming directionally solidified castings.
  • the long contact time of molten metal with the mold to allow directional solidification, the high temperatures required for casting titanium alloys, and the reactive metal titanium can produce severe metal-mold reactions that must be minimized in order to produce an acceptable casting.
  • the titanium alloys of interest for casting in the method of this invention are the gamma titanium aluminide based alloys
  • Gamma titanium aluminides are well known being characterized by a tetragonal crystal structure, and are comprised of about 48 to 58 atom percent aluminum.
  • Gamma titanium aluminide alloys comprised of a minor amount of alpha-2 phase are comprised of as low as 40 atom percent aluminum. Additional elements, for example, chromium, vanadium, niobium, tantalum, silicon, and gallium have been added to gamma titanium aluminide alloys as shown for example in U.S.
  • the low ductility of the gamma titanium aluminides at room temperature has been the major limitation to forming components of the alloys. It is well known that oxygen is an interstitial contaminant in gamma titanium aluminides that contributes to the room temperature brittleness of the alloy.
  • the molten zone is held in place by surface tension forces so that a crucible is unnecessary for holding the casting as it directionally solidifies.
  • the floating zone method of forming directionally solidified castings is comparatively slow, energy intensive, and limited in the shapes that can be formed.
  • the method of this invention provides for directional solidification vacuum or protective atmosphere casting of gamma titanium aluminide alloys.
  • the directional solidification casting is performed in a mold comprised of a chill and a sidewall means extending from the chill to form a cavity for holding a molten metal.
  • a melt of the gamma titanium aluminide alloy comprised of an effective amount of a metal from the group consisting of niobium, tantalum, tungsten, and molybdenum to reduce oxygen pickup in the melt is formed in the cavity, the sidewall means having at least an inner liner of a calcia refractory facing the melt.
  • the melt is heated in a thermal gradient sufficient to cause directional solidification of the melt from the chill.
  • the melt is comprised of about 2 to 12 atom percent niobium, and most preferably about 4 to 8 atom percent niobium.
  • the method of this invention can be used for directional solidification casting of the gamma titanium aluminide alloys.
  • the casting is performed in a vacuum or protective atmosphere that does not react with the molten metal such as argon or helium.
  • a melt is formed in a mold and heated in a thermal gradient to form a directionally solidified crystal structure of columnar grains growing from the surface of a chill in the mold.
  • the molten portions of the casting are exposed to the mold sidewalls for an extended period of time during which the highly reactive titanium aluminide alloy melt can react with the sidewalls and pickup contaminants such as oxygen.
  • FIG. 1 is a cross-section of a directional solidification casting assembly 20.
  • Casting assembly 20 is comprised of a chill 2, a cylindrical sidewall 4, and a heating means 10.
  • the casting assembly 20 is located in a vessel, not shown, of conventional construction suitable for containing a vacuum or protective atmosphere.
  • Chill 2 is a metal body capable of solidifying molten titanium or titanium alloys without reacting with the molten metal.
  • a suitable chill 2 is comprised of molybdenum or copper that is water cooled by conventional means not shown.
  • Sidewall 4 is generally cylindrical and extends from chill 2 to form a cylindrical cavity 6 for holding molten metal 12.
  • sidewall 4 is sealed against chill 2 by a ceramic seal 8, of conventional material known in the art for forming a high temperature seal of ceramic to metal.
  • a suitable ceramic seal 8 can be formed by pouring a ceramic slurry comprised of alumina powder in a binder comprised of about 8.3 weight percent K2O, about 20.8 weight percent silica, and about 70.9 weight percent water where sidewall 4 contacts chill 2. The ceramic slurry is dried and baked at about 400°C to remove the liquid.
  • Sidewall 4 is formed to have at least an inner liner of a calcia refractory adjacent the molten metal 12.
  • a suitable calcia refractory is comprised of calcia and may contain other ceramics that do not react with molten titanium or titanium alloys.
  • a suitable calcia refractory is comprised of calcia and calcium floride, available from Calceed Co., Ltd., Japan.
  • sidewall 4 is formed from a high-purity calcia, for example, described in U.S. Patent 4,710,481, incorporated herein by reference. Sidewall 4 may be formed solely of the calcia refractory.
  • chill 2 and sidewall 4 are shown in Fig. 1 as bodies defining a cylindrical cavity 6, chill 2 and sidewall 4 can be formed to define cavities of any desired configuration to form components, such as, medical prostheses, pump components, gas turbine components such as turbine blades, airframe components, or heat exchangers.
  • Heating means 10 is a conventional heating means for heating above the liquidus temperature of gamma titanium aluminide alloys, such as an induction heater or tungsten resistance heater. Heating means 10 heats the sidewall 4 above the liquidus temperature of the melt and maintains melt 12 in a molten state.
  • Melt 12 of a gamma titanium aluminide alloy is formed by conventional means such as skull melting and pouring the melt into cavity 6, or melting a solid charge placed in cavity 6 using heating means 10. The skull melting and pouring are performed in the non-oxidizing atmosphere or vacuum surrounding assembly 20. Additional information about skull melting can be found for example in, "Vacuum Arc Skull Melting and Casting," Metals Handbook, 9th Edition, Vol. 15, Casting, ASM International, 1988, pp.
  • a conventional directional solidification casting furnace is shown, for example in, "Directional and Monocrystal Solidification,” Metals Handbook, 9th Edition, Vol. 15, Casting, ASM International, 1988, pp. 319 to 323, incorporated herein by reference.
  • Assembly 20 is supported by rod 16 operatively connected to conventional means, not shown, for controlled movement of assembly 20 in the direction of arrow 18.
  • Heating means 10 maintains the temperature of melt 12 above the liquidus temperature of the gamma titanium aluminide alloy.
  • a thermal gradient exists between chill surface 2 and melt 12 that causes grains to nucleate and grow on chill surface 2.
  • Mold assemble 20 is maintained in the initial position shown in FIG. 1 for a period of time to allow the grains to nucleate and grow so that the most favorably oriented grains are established. Grains with a preferred growth direction normal to the chill surface grow and crowd out the other grains.
  • the mold assembly 20 is withdrawn from heater 10 in the direction of arrow 18 at a controlled rate.
  • the rate of withdrawal of mold assembly 20 from heater 10 is controlled to allow for directional solidification of solid 14 forming columnar grains 15 extending from the chill surface 2 to melt 12.
  • a thermal gradient having a hot zone above the liquidus temperature of the melt, and a zone below the solidus temperature of the alloy is formed at the interface of solid 14 and liquid 12.
  • the thermal gradient is passed from one end of the melt to the other at a rate that maintains the steady growth of the dendrites 15.
  • a suitable thermal gradient is about 50° to 300°C per inch above the melting temperature of the gamma titanium aluminide alloy, and a suitable travel rate for the thermal gradient is about 1 to 20 inches per hour.
  • the first example is performed to show the level of oxygen pickup in a melt of gamma titanium aluminide alloys obtained by conventional skull melting.
  • gamma titanium aluminide alloys obtained by conventional skull melting.
  • Several charges of gamma titanium aluminide alloys were formed from high-purity titanium sponge about 99.9% pure, high-purity aluminum about 99.99% pure, and high-purity chromium and niobium about 99.9 percent pure.
  • the charges were placed in a water cooled copper crucible arc melting furnace obtained from Retech, Inc., Ca..
  • the charges were melted under a protective atmosphere of argon by arc melting using the skull melting method. After the charge was melted the arc was extinguished and the charge was allowed to solidify in the copper crucible.
  • a calcia crucible comprised of 99 percent purity fused calcia was obtained from Mitsui Zosen Incorporated (USA), New York.
  • Two gamma titanium aluminide alloys were melted by induction heating in the calcia crucibles.
  • Three to four charges were melted in each crucible with a slight variation in the charging procedure for each melt.
  • the charges were formed from high-purity titanium sponge about 99.9% pure, high-purity aluminum about 99.99% pure, and high-purity chromium and niobium about 99.9 percent pure.
  • the charges were formed by placing pieces of the elements in the crucible in the following order: Melt 1; chromium, niobium, aluminum, titanium, Melt 2; titanium, aluminum, niobium, chromium, Melt 3; titanium, aluminum, niobium, chromium, Melt 4; niobium, chromium, aluminum, titanium, Melt 5; all four elements melted together, and Melts 6 and 7; niobium and aluminum melted first followed by chromium and titanium.
  • Two gamma titanium aluminide alloy rods comprised of about 46 atom percent aluminum, 10 atom percent niobium, and the balance titanium were prepared by the well known arc melting and drop casting method.
  • a directionally solidified casting of the gamma titanium aluminide was formed in a mold assembly as shown in FIG. 1 comprised of a tungsten-resistance heater and a water-cooled molybdenum chill surface.
  • a calcia sidewall for the mold was obtained from Mitsui Zosen Incorporated (USA), New York.
  • the sidewall had an inner diameter of about 2.5 centimeters and a length of about 12.5 centimeters.
  • the sidewall was sealed on the molybdenum chill surface by an alumina seal.
  • the rods about 1.9 centimeters in diameter and 5 centimeters in length, were placed in the mold.
  • the rods were melted by the tungsten-resistance heater encircling the sidewall, and the mold assembly was withdrawn from the tungsten-resistance heater at a rate of about 35 centimeters per hour to provide directional solidification of the melt.
  • a directionally solidified rod of about 2.5 centimeters in diameter and 6.35 centimeters in length having a columnar grain structure with grains about 0.25 centimeter in diameter was formed. Chemical analysis of the directionally solidified rod showed the oxygen concentration to be abut 1700 parts per million.
  • the directionally solidified rod was tested by the well known four point bending method to determine the toughness and in conventional tensile testing to determine the yield strength and plastic fracture strain of the directionally solidified material.
  • the directionally solidified rod had a toughness of about 18 MPa ⁇ m, a yield strength of about 675 MPa, and a plastic fracture strain of about 0.75 percent.
  • the directionally solidified rod was heat treated at about 1275°C for 2 hours.
  • the tensile testing was performed at room temperature.
  • the yield strength was again measured at 875°C to be about 580 MPa, and the plastic fracture strain was about 10 percent.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP92306862A 1991-08-29 1992-07-28 Méthode pour la coulée par solidification directionnelle de l'aluminure de titane Withdrawn EP0530968A1 (fr)

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US738759 1991-08-29

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0554198A1 (fr) * 1992-01-30 1993-08-04 Howmet Corporation Pièces coulées en superalliage, résistants à l'oxydation
GB2294001A (en) * 1994-10-14 1996-04-17 Honda Motor Co Ltd Thixocasting semi-molten casting material
EP0761831A1 (fr) * 1995-08-23 1997-03-12 Tanaka Denshi Kogyo Kabushiki Kaisha Fil d'or fin pour connexion
DE102005015862A1 (de) * 2005-04-07 2006-10-12 Ald Vacuum Technologies Gmbh Verfahren zum Herstellen einer Vielzahl von insbesondere aus Titanaluminid bestehenden Bauteilen und Vorrichtung zur Durchführung dieses Verfahrens
US8708033B2 (en) 2012-08-29 2014-04-29 General Electric Company Calcium titanate containing mold compositions and methods for casting titanium and titanium aluminide alloys
DE102012222745A1 (de) 2012-12-11 2014-06-12 MTU Aero Engines AG Einkristalline Turbinenschaufel aus Titanaluminid
US8858697B2 (en) 2011-10-28 2014-10-14 General Electric Company Mold compositions
US8906292B2 (en) 2012-07-27 2014-12-09 General Electric Company Crucible and facecoat compositions
US8932518B2 (en) 2012-02-29 2015-01-13 General Electric Company Mold and facecoat compositions
US8992824B2 (en) 2012-12-04 2015-03-31 General Electric Company Crucible and extrinsic facecoat compositions
US9011205B2 (en) 2012-02-15 2015-04-21 General Electric Company Titanium aluminide article with improved surface finish
US9192983B2 (en) 2013-11-26 2015-11-24 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
US9511417B2 (en) 2013-11-26 2016-12-06 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
US9592548B2 (en) 2013-01-29 2017-03-14 General Electric Company Calcium hexaluminate-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
CN107962170A (zh) * 2016-10-19 2018-04-27 中国科学院金属研究所 一种各向异性生物医用定向凝固镁锌合金材料制备方法
US10391547B2 (en) 2014-06-04 2019-08-27 General Electric Company Casting mold of grading with silicon carbide
US10421121B2 (en) 2015-02-03 2019-09-24 Ihi Corporation Method of manufacturing Ni alloy casting and Ni alloy casting
CN112760527A (zh) * 2020-12-22 2021-05-07 衢州学院 一种高压定向凝固材料及其方法
CN114406246A (zh) * 2022-03-10 2022-04-29 湖南东方钪业股份有限公司 一种铝钪中间合金钪析沉富集用控温缓凝铸造模及工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016055013A1 (fr) * 2014-10-09 2016-04-14 南京理工大学 Matériau monocristallin composite intermétallique à base de tial et son procédé de préparation

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US4294615A (en) * 1979-07-25 1981-10-13 United Technologies Corporation Titanium alloys of the TiAl type
EP0092496A1 (fr) * 1982-03-01 1983-10-26 United Technologies Corporation Moule avec sections d'amorçage et de sélection pour la coulée par solidification directionnelle
US4710481A (en) * 1985-09-13 1987-12-01 Mitsui Engineering & Shipbuilding Co., Ltd. Method for melting Ti or a high-Ti alloy in CaO refractories
EP0406638A1 (fr) * 1989-07-03 1991-01-09 General Electric Company Alliages de gamma titane aluminium modifié par du chrome et du tantale et procédé de fabrication

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JPS63227728A (ja) * 1987-03-16 1988-09-22 Furukawa Electric Co Ltd:The 溶解ルツボおよび溶解法
JPS6418561A (en) * 1987-07-14 1989-01-23 Mitsubishi Metal Corp Production of active metal having unidirectional solidified structure and its alloy casting
JPH01287243A (ja) * 1988-05-13 1989-11-17 Nippon Steel Corp Ｍｎ、Ｎｂを含有するＴｉ−Ａｌ系金属間化合物とその製造方法
US4879092A (en) * 1988-06-03 1989-11-07 General Electric Company Titanium aluminum alloys modified by chromium and niobium and method of preparation
US4897127A (en) * 1988-10-03 1990-01-30 General Electric Company Rapidly solidified and heat-treated manganese and niobium-modified titanium aluminum alloys
JPH03193837A (ja) * 1989-12-22 1991-08-23 Honda Motor Co Ltd 高温耐酸化性金属間化合物ＴｉＡｌ系合金

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294615A (en) * 1979-07-25 1981-10-13 United Technologies Corporation Titanium alloys of the TiAl type
EP0092496A1 (fr) * 1982-03-01 1983-10-26 United Technologies Corporation Moule avec sections d'amorçage et de sélection pour la coulée par solidification directionnelle
US4710481A (en) * 1985-09-13 1987-12-01 Mitsui Engineering & Shipbuilding Co., Ltd. Method for melting Ti or a high-Ti alloy in CaO refractories
EP0406638A1 (fr) * 1989-07-03 1991-01-09 General Electric Company Alliages de gamma titane aluminium modifié par du chrome et du tantale et procédé de fabrication

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0554198A1 (fr) * 1992-01-30 1993-08-04 Howmet Corporation Pièces coulées en superalliage, résistants à l'oxydation
GB2294001A (en) * 1994-10-14 1996-04-17 Honda Motor Co Ltd Thixocasting semi-molten casting material
GB2294001B (en) * 1994-10-14 1998-06-03 Honda Motor Co Ltd Thixocasting semi-molten casting material, and process for producing the same
US5925199A (en) * 1994-10-14 1999-07-20 Honda Giken Kogyo Kabushiki Kaisha Process for producing a thixocast semi-molten material
EP0761831A1 (fr) * 1995-08-23 1997-03-12 Tanaka Denshi Kogyo Kabushiki Kaisha Fil d'or fin pour connexion
US8042599B2 (en) 2005-04-07 2011-10-25 Ald Vacuum Technologies Gmbh Method for producing a multitude of components made of, in particular, titanium aluminide, and device for carrying out this method
DE102005015862A1 (de) * 2005-04-07 2006-10-12 Ald Vacuum Technologies Gmbh Verfahren zum Herstellen einer Vielzahl von insbesondere aus Titanaluminid bestehenden Bauteilen und Vorrichtung zur Durchführung dieses Verfahrens
US8858697B2 (en) 2011-10-28 2014-10-14 General Electric Company Mold compositions
US9011205B2 (en) 2012-02-15 2015-04-21 General Electric Company Titanium aluminide article with improved surface finish
US9802243B2 (en) 2012-02-29 2017-10-31 General Electric Company Methods for casting titanium and titanium aluminide alloys
US8932518B2 (en) 2012-02-29 2015-01-13 General Electric Company Mold and facecoat compositions
US8906292B2 (en) 2012-07-27 2014-12-09 General Electric Company Crucible and facecoat compositions
US8708033B2 (en) 2012-08-29 2014-04-29 General Electric Company Calcium titanate containing mold compositions and methods for casting titanium and titanium aluminide alloys
US8992824B2 (en) 2012-12-04 2015-03-31 General Electric Company Crucible and extrinsic facecoat compositions
US9803923B2 (en) 2012-12-04 2017-10-31 General Electric Company Crucible and extrinsic facecoat compositions and methods for melting titanium and titanium aluminide alloys
DE102012222745A1 (de) 2012-12-11 2014-06-12 MTU Aero Engines AG Einkristalline Turbinenschaufel aus Titanaluminid
US9592548B2 (en) 2013-01-29 2017-03-14 General Electric Company Calcium hexaluminate-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
US9192983B2 (en) 2013-11-26 2015-11-24 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
US9511417B2 (en) 2013-11-26 2016-12-06 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
US10391547B2 (en) 2014-06-04 2019-08-27 General Electric Company Casting mold of grading with silicon carbide
US10421121B2 (en) 2015-02-03 2019-09-24 Ihi Corporation Method of manufacturing Ni alloy casting and Ni alloy casting
CN107962170A (zh) * 2016-10-19 2018-04-27 中国科学院金属研究所 一种各向异性生物医用定向凝固镁锌合金材料制备方法
CN112760527A (zh) * 2020-12-22 2021-05-07 衢州学院 一种高压定向凝固材料及其方法
CN112760527B (zh) * 2020-12-22 2021-08-17 衢州学院 一种高压定向凝固材料及其方法
CN114406246A (zh) * 2022-03-10 2022-04-29 湖南东方钪业股份有限公司 一种铝钪中间合金钪析沉富集用控温缓凝铸造模及工艺

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