EP1287173B1 - Composant a base d'alliages gamma-tial comportant des zones de structure graduee - Google Patents

Composant a base d'alliages gamma-tial comportant des zones de structure graduee Download PDF

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Publication number
EP1287173B1
EP1287173B1 EP01936369A EP01936369A EP1287173B1 EP 1287173 B1 EP1287173 B1 EP 1287173B1 EP 01936369 A EP01936369 A EP 01936369A EP 01936369 A EP01936369 A EP 01936369A EP 1287173 B1 EP1287173 B1 EP 1287173B1
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Prior art keywords
microstructure
tial
lamellar
produced
area
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EP01936369A
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German (de)
English (en)
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EP1287173A1 (fr
Inventor
Volker GÜTHER
Andreas Otto
Helmut Prof. Dr. Mont. Clemens
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GfE Metalle und Materialien GmbH
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GfE Metalle und Materialien GmbH
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/22—Non-oxide ceramics
    • F05D2300/228—Nitrides
    • F05D2300/2284—Nitrides of titanium

Definitions

  • the invention relates to components based on intermetallic ⁇ -TiAl alloys with a graded microstructure transition between spatially separated regions each having a different microstructure and a method for the production thereof.
  • Intermetallic ⁇ -TiAl alloys have received much attention in recent years due to their combination of unique material properties. Their advantageous mechanical and thermophysical properties with low specific weight recommend their use in the aerospace industry. The high temperature and corrosion resistance makes the material interesting for fast moving components in machines, eg for valves in internal combustion engines or for blades in gas turbines.
  • the currently used technical alloys based on ⁇ -TiAl have a multiphase structure and, in addition to the ordered tetragonal ⁇ -TiAl as the main phase, contain the ordered hexagonal ⁇ 2 -Ti 3 Al, typically with 5-15% by volume.
  • Refractory metals as alloying elements can lead to the formation of a metastable body-centered cubic phase, which occurs either as ⁇ phase (disordered) or as B2 phase (ordered). These alloying additives improve the oxidation resistance and creep resistance.
  • Si, B and C are used in small quantities for grain refining of the cast structure. Corresponding C levels can lead to precipitation hardening.
  • alloying elements Cr, Mn and V increase the room temperature ductility of the otherwise very brittle TiAl.
  • alloy development has resulted in a number of different alloy variants, which can generally be described by the following empirical formula: Ti Al (44-48) (Cr, Mn, V) 0.5-5 (Zr, Cu, Nb, Ta, Mo, W, Ni) 0.1-10 (Si, B, C, Y) O, 05-1 (Data in atomic%)
  • TiAl alloys are usually prepared by multiple melting in a vacuum arc furnace as ingots (VAR - Vacuum Arc Remelting).
  • VAR - Vacuum Arc Remelting a vacuum arc furnace
  • the production of alloys based on ⁇ -TiAl by means of gravity die casting from a cold wall induction or plasma furnace or by inert gas atomization from a cold wall crucible to ⁇ -TiAl powder and powder metallurgy further processing technically realized.
  • the ⁇ -TiAl melted via the ingot route usually has a coarse-grained structure, the grains being essentially composed of ⁇ -TiAl / ⁇ 2 -Ti 3 Al lamellae (see FIG.
  • the alloy composition and depending on the type and rate of solidification of the melt to solid base alloy and the subsequent cooling can be in the cast structure, a wide range of more or less homogeneous small and / or large grain diameters, but also of fine or to achieve coarse lamellar structure within a grain of the alloy.
  • the range of structure-related mechanical properties of a ⁇ -TiAl alloy is known to be substantially extended by massive forming at temperatures in the range between 900 ° C and 1400 ° C compared to cast structures. Massive forming produces a dynamically recrystallized fine-grained microstructure.
  • the basic structure types can be described near- ⁇ microstructure (globular ⁇ grains with ⁇ 2 phase at grain boundaries and triple points), duplex Structures (globular ⁇ grains and lamellar ⁇ 2 / ⁇ at approximately equal proportions), nearly lamellar microstructures (grains of ⁇ 2 / ⁇ lamellae and occasionally globular ⁇ grains) and fully lamellar microstructures (grains of ⁇ 2 / ⁇ - Slats) (see Fig. 2).
  • Fine-grained near- ⁇ and duplex microstructures have a good room temperature ductility, a high elongation at break and a high tensile strength and thus a high fatigue strength, but at the same time a low creep strength and a low fracture toughness.
  • microstructures with comparatively coarser grains and with a pronounced lamellar structure show significantly better creep strength and a higher fracture toughness, but on the other hand also lower fatigue strength and elongation at break.
  • the DE-C-43 18 424 C2 describes a process for the production of moldings from ⁇ -TiAl alloys, for example also in the form of valves and valve plates for engines.
  • a casting blank is first deformed in the temperature range of 1050 ° C to 1300 ° C under quasi-isothermal conditions with high degree of deformation, the part then cooled and finally at temperatures of 900 ° C to 1100 ° C at low forming speed of 10 -4 to 10 -1 / s to the near-net shape molding superplastic reshaped.
  • the process is multi-step and therefore technically complex.
  • valves for internal combustion engines and rotor blades for gas turbines for the individual component areas different, sometimes very different material properties are required, especially with regard to their thermo-mechanical properties.
  • This is usually met by the fact that a component is composed of areas of different materials, eg by means of force and / or material joining.
  • Valves for internal combustion engines are made today, for example, for the shaft and for the plate area different steel grades, the parts are joined together by friction welding.
  • thermo-mechanical material properties required for a valve stem are formed in this subarea.
  • the extrusion process for the part is "broken off" in a die with a conical transition between the inlet and outlet regions at the time that a finished valve with twice reshaped, slender shank region formed with once formed, thick plate area and with a cone-shaped transition zone.
  • the microstructure, in particular grain shape and size, between plate and shaft area change graded in a manner that is determined by the forming parameters of the two forming steps. This method also includes several forming steps and is therefore complicated and expensive.
  • Object of the present invention is, for components of alloys based on ⁇ -TiAl, which have local areas with different thermo-mechanical requirement profiles in the final state and should have a transition zone with respect to the material properties, a relation to the
  • the lamellar cast structure consisting of ⁇ 2 / ⁇ lamellae has been produced by directed solidification of a molten alloy.
  • the near- ⁇ structure, duplex structure or fine-lamellar structure has preferably been produced in the at least one further region by massive deformation and optionally by a subsequent treatment from the cast structure.
  • the object is further achieved by a method for the production of such components, wherein in a first step in a conventional manner, a suitable TiAl melt is produced, in a second step, the TiAl melt by directed Solidification is transferred to a semi-finished product, which has a lamellar, consisting of ⁇ 2 / ⁇ -TiAl lamellae cast structure, and in a third step in a portion or in partial areas of the semi-finished lamellar, consisting of ⁇ 2 / ⁇ -TiAl lamellae Cast structure by massive forming in a temperature range of 900 ° C to 1400 ° C in a near- ⁇ -structure, duplex structure or fine-lamellar structure is transferred.
  • a pore-free, cylindrical semifinished product is produced from the TiAl melt by means of continuous casting, which is then massively shaped by extrusion of a rod region.
  • a cylindrical semifinished product is produced from the TiAl melt by means of centrifugal casting free of voids, which is then massively formed by extrusion of a rod region.
  • regions of high tensile strength, ductility and fatigue strength can be realized with high fracture toughness and high creep resistance in one and the same component.
  • a significant advantage of the components according to the invention is that over the selection of manufacturing steps in comparison to the prior art, a significant saving in manufacturing costs can be achieved.
  • the economic advantage results from the technical knowledge that in such components can be dispensed with a multiple forming of the semifinished product with cast structure.
  • the special casting method according to the invention which is described in more detail below, already allows unforeseen advantageous material properties for comparatively large variation widths of property combinations, which are thus individually adapted to the respective material requirement.
  • a semi-finished product In this way, by means of massive forming, the cast structure is set to achieve a dynamically recrystallised structure with thermo-mechanical properties which deviate greatly from the properties of the cast semi-finished product.
  • the properties of the dynamically recrystallized structure can also be varied by adjusting the process parameters.
  • intermetallic ⁇ -TiAl alloy covers a wide field of single alloys.
  • An essential alloying range is the molecular formula Ti Al (44-48) (Cr, Mn, V) 0.5-5 (Zr, Cu, Nb, Ta, Mo, W, Ni) 0.1-10 (Si, BC, Y) 0.05-1 (Data in atomic%) covered.
  • the semifinished product in the form of the cast blank is subsequently massively formed in the temperature range between 900 ° C. and 1400 ° C. by extrusion or by means of an equivalent forming process and brought into a form which is matched to the dimensions of the end product.
  • the bars are extruded over only part of their total length in an extrusion die of such profile dimensions which at least approximately correspond to the final dimensions of the component in the formed area, eg dimensions of a valve for internal combustion engines with conical transition between stem and plate area.
  • the extruded mold has a conically tapered cross-section between the inlet region to the outlet region.
  • the semi-finished product is increasingly transformed in the tapered die area and thus continuously transferred from the microstructure state of the cast structure in the recrystallized microstructure achieved by extrusion.
  • the already existing empirical knowledge makes it possible for a person skilled in the art to change specific thermo-mechanical properties of the material by means of appropriate forming parameters within material-related limits and to optimize them for special requirements.
  • Preferred components according to the invention are valves for internal combustion engines. This applies in particular to emerging future applications. While previously engine valves are usually controlled via a camshaft and used as a material different steel grades, the current development is in the direction of electromagnetic or pneumatic single-valve control. However, lightweight valves are required for this, which must have sufficient strength and corrosion resistance at high temperatures, in extreme cases up to 850 ° C in the plate area.
  • Valves are stressed in the shaft area at rather moderate temperatures due to strong alternating loads (fatigue).
  • the requirements for the material in terms of strength and ductility are correspondingly high there.
  • these locally different thermomechanical properties are achieved in an outstanding manner.
  • thermomechanical properties are required in the base of the blade as in the peripheral region of the blade.
  • a TiAl starting alloy of composition Ti-46Al-8,5Nb- (1-3) (Ta, Si, B, C, Y) (in atomic%) is melt metallurgically made into a bar stock having a diameter of 40 mm, which corresponds approximately to the diameter of a valve disk.
  • the alloy is made by mixing titanium sponge, Al granules and AlNbTaSiBYC multi-alloy, in which the atomic ratios between the alloying elements Nb, Ta, Si, B, C and Y correspond to those in the final TiAl alloy. From the material mixture, a stable rod is pressed, which is used as Abschmelzelektrode in a vacuum arc furnace and remelted into a primary ingot.
  • the primary ingot has an inhomogeneous alloy composition and is therefore remelted and homogenized in a cold hearth in a skull of inherent material contained in a water-cooled copper crucible.
  • a heated with a plasma torch the melt flows into a strand extraction device, at the upper end of a third homogenization in the molten phase by means of a cold wall Indutationstrainels.
  • the molten TiAl alloy is drawn down as a block or rod, the material solidifies pore-free directionally.
  • the in process is shown schematically in Fig. 3 and is of AL Dowson et al.
  • the coil is dimensioned so that the energy is sufficient for the complete melting of the alloy located in the coil.
  • the semi-finished product obtained in this way has a lamellar cast structure with colony sizes of the lamellae packs between 100 ⁇ m and 500 ⁇ m, but at the same time excellent material homogeneity.
  • the individual rods thus obtained as semi-finished products are divided into cylindrical segments, brought under protective gas to a specific temperature of 1200 ° C. for forming and pressed out in the protective gas by extrusion into a heated die with a valve shape.
  • the forming ratio in the shank area is approx.
  • the present invention is not limited to the example described above, but rather the invention also includes components for other, not mentioned applications, in which a corresponding structure of structure is required or advantageous for the application.
  • the material ⁇ -base TiAl alloy is not limited to the explicitly mentioned alloy compositions.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Ceramic Products (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (11)

  1. Composant fabriqué en une pièce constitué d'un alliage intermétàllique à base de γ-TiAl avec une transition de structure progressive entre les zones spatialement adjacentes, respectivement, de structures différentes, caractérisé en ce qu'il présente au moins dans une zone, une structure lamellaire produite par déformation en masse constituée de lamelles de α2/γ qui a été produite par solidification ciblée d'un alliage fondu, et dans au moins une autre zone, une structure produite par déformation en masse de type quasi-γ, une structure duplexe ou une structure fine lamellaire, sachant qu'entre ces zones, une zone de transition présentant une structure progressive est présente, dans laquelle la structure coulée lamellaire passe peu à peu dans l'autre structure citée.
  2. Composant selon la revendication 1, caractérisé en ce que la structure quasi-γ, la structure duplexe ou la structure fine lamellaire a été fabriquée au moins dans une autre zone, par déformation massive et traitement secondaire à partir de la structure de coulée.
  3. Composant selon la revendication 1 ou 2, caractérisé en ce qu'il s'agit d'un produit semi-ouvré cylindrique obtenu à partir de la masse fondue, au moyen de coulée continue sous forme de barre sans pores, qui est ensuite déformé massivement par presse à filer dans une zone de tige.
  4. Composant selon la revendication 1 ou 2, caractérisé en ce qu'il s'agit d'un produit semi-ouvré cylindrique obtenu à partir de la masse fondue, au moyen de coulée centrifuge sans cavités, qui est ensuite déformé massivement par presse à filer dans une zone de tige.
  5. Composant selon au moins l'une des revendications 1 à 4, caractérisé en ce que l'alliage correspond à la formule élémentaire :

            TiAl(44-48) (Cr, Mn, V)0,5-5 (Zr, Cu, Nb, Ta, Mo, W, Ni)0,1-10 (Si, B, C, Y)0,05-1

    exprimée en % atomiques.
  6. Composant selon au moins l'une des revendications 1 à 5, caractérisé en ce qu'il est une soupape pour moteurs à combustion.
  7. Procédé de fabrication de composants selon la revendication 1, caractérisé en ce que dans une première étape, de manière habituelle, une masse fondue de TiAl est produite, dans une deuxième étape, la masse fondue de TiAl est transformée en un produit semi-ouvré par solidification ciblée qui présente une structure coulée lamellaire constituée de lamelles de α2/γ-TiAl lamellaire et dans une troisième étape, dans une zone partielle ou dans des zones partielles du produit semi-ouvré, la structure coulée constituée de lamelles de α2/γ-TiAl est transformée par formage massif dans une plage de température de 900° C à 1400° C en une structure quasi-γ, une structure duplexe ou une structure lamellaire fine.
  8. Procédé selon la revendication 7, caractérisé en ce que le produit semi-ouvré sans pore, de forme cylindrique est fabriqué à partir de masse fondue de TiA1 par coulée en continu, et est ensuite formé en masse par extrusion d'une zone en tige.
  9. Procédé selon la revendication 7, caractérisé en ce qu'un produit semi ouvré de forme cylindrique sans cavité est fabriqué à partir de la masse fondue de TiAl par coulée centrifuge et est ensuite formé en masse par extrusion d'une zone en tige.
  10. Procédé selon au moins l'une des revendications 7 à 9, caractérisé en ce l'alliage de TiAl correspond à la formule élémentaire :

            TiAl(44-48) (Cr, Mn, V)0,5-5 (Zr, Cu, Nb, Ta, Mo, W, Ni) 0,1-10 (Si, B, C, Y)0,05-1

    exprimée en % atomiques.
  11. Procédé selon au moins l'une des revendications 7 à 10, caractérisé en ce qu'une soupape pour moteurs à combustion est fabriquée.
EP01936369A 2000-05-17 2001-05-17 Composant a base d'alliages gamma-tial comportant des zones de structure graduee Expired - Lifetime EP1287173B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10024343A DE10024343A1 (de) 2000-05-17 2000-05-17 Bauteil auf Basis von gamma-TiAl-Legierungen mit Bereichen mit gradiertem Gefüge
DE10024343 2000-05-17
PCT/EP2001/005621 WO2001088214A1 (fr) 2000-05-17 2001-05-17 Composant a base d'alliages gamma-tial comportant des zones de structure graduee

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EP1287173A1 EP1287173A1 (fr) 2003-03-05
EP1287173B1 true EP1287173B1 (fr) 2008-01-16

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US (1) US20040045644A1 (fr)
EP (1) EP1287173B1 (fr)
JP (1) JP2003533594A (fr)
AT (1) ATE384146T1 (fr)
AU (1) AU2001262295A1 (fr)
DE (2) DE10024343A1 (fr)
ES (1) ES2298238T3 (fr)
WO (1) WO2001088214A1 (fr)

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ATE384146T1 (de) 2008-02-15
DE10024343A1 (de) 2001-11-22
US20040045644A1 (en) 2004-03-11
AU2001262295A1 (en) 2001-11-26
JP2003533594A (ja) 2003-11-11
ES2298238T3 (es) 2008-05-16
WO2001088214A1 (fr) 2001-11-22
DE50113507D1 (de) 2008-03-06
EP1287173A1 (fr) 2003-03-05

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