CA2645843A1 - Titanium aluminide alloys - Google Patents
Titanium aluminide alloys Download PDFInfo
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- CA2645843A1 CA2645843A1 CA002645843A CA2645843A CA2645843A1 CA 2645843 A1 CA2645843 A1 CA 2645843A1 CA 002645843 A CA002645843 A CA 002645843A CA 2645843 A CA2645843 A CA 2645843A CA 2645843 A1 CA2645843 A1 CA 2645843A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- 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
Abstract
The invention relates to alloys based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl). An alloy according to the invention has the composition Ti - (38 to 42 atom %) Al - (5 to 10 atom %) Nb, wherein the composition comprises composite lamella structures with B19 phase and .beta. phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the .beta. phase in each lamella is between 0.05 and 20, in particular between 0.1 and 10.
The alloys are characterized by a high rigidity and creep resistance with simultaneously high ductility and fracture toughness.
The alloys are characterized by a high rigidity and creep resistance with simultaneously high ductility and fracture toughness.
Description
Titanium aluminide alloys Description The invention relates to alloys based on titanium aluminide, in particular made through the use of casting or powder metallurgical processes, preferably based on y (TiAI).
Titanium aluminide alloys are characterized by a low density, a high rigidity and good corrosion resistance. In the fixed state, they have domains with hexagonal (a), two-phase structures (a +(3) and cubically body-centered (3 phase and/or y phase.
For industrial practice, alloys based on an intermetallic phase y(TiAI) with a tetragonal structure and contain minority shares of intermetallic phase a2(Ti3AI) with hexagonal structure in addition to the majority phase y (TiAI) are particularly interesting. This y titanium aluminide alloys are characterized by properties like low density (3.85 - 4.2 g/cm3), high elastic modules, high rigidity and creep resistance up to 700 C, which make them attractive as a lightweight construction material for high-temperature applications. Examples of this are turbine buckets in aircraft engines and in stationary gas turbines, valves for engines and hot gas ventilators.
In the technically important area of alloys with aluminum content between 45 atom % and 49 atom %, a series of phase conversions occur during the solidification from the cast and during the subsequent cooling. The solidification can either take place completely via the (3 mixed crystal with a cubically body-centered structure (high temperature phase) or in two peritectic reactions, in which the a mixed crystal with hexagonal structure and the y phase participate.
Furthermore, it is known that aluminum in y titanium aluminide alloys causes an increase in the ductility and the oxidation resistance.
Moreover, element Niob (Nb) leads to an increase in the rigidity, creep resistance, oxidation resistance, but also the ductility. With the element boron, which is practically insoluble in the y phase, a grain refinement can be achieved in both the as-cast state and after the reshaping with subsequent heat treatment in the a area. An increased share of (3 phase in the structure as a result of low aluminum contents and high concentrations of (3 stabilizing elements can lead to rough dispersion of this phase and can cause deterioration of the mechanical properties.
The mechanical properties of titanium aluminide alloys are strongly anisotropic due to their deformation and breaking behavior but also due to the structural anisotropy of the preferably set lamellar structure or duplex structure. Casting processes, different powder-metall-urgical and reshaping processes and combinations of these production processes are used for a targeted setting of structure and texture in the production of components made of titanium aliminides.
Moreover, a titanium aluminide alloy, which has a structurally and chemically homogeneous structure, is known from EP 1 015 650 B1.
The majority phases y(TiAI) and a2 (Ti3AI) are hereby distributed in a finely disperse manner. The disclosed titanium aluminide alloy with an aluminum content of 45 atom % is characterized by extraordinarily good mechanical properties and high temperature properties.
Titanium aluminides based on y(TiAl) are characterized in general by relatively high rigidities, high elastic modules, good oxidation and creep resistance with simultaneously lower density. Based on these properties, TiAI alloys should be used as high temperature materials.
These types of applications are heavily impaired through the very low plastic malleability and the low fracture toughness. Rigidity and malleability, as with many other materials, behave hereby inversely.
The technically interesting high-strength alloys are thereby often particularly brittle. Comprehensive examinations for the optimization of the structure were performed in order to eliminate these disadvantageous properties.
The previously developed structure types can be roughly categorized into a) coaxial gamma structures, b) duplex structures and c) lamellar structures. The currently achieved development state is represented in detail for example in:
= Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, C.T. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, pg.
Titanium aluminide alloys are characterized by a low density, a high rigidity and good corrosion resistance. In the fixed state, they have domains with hexagonal (a), two-phase structures (a +(3) and cubically body-centered (3 phase and/or y phase.
For industrial practice, alloys based on an intermetallic phase y(TiAI) with a tetragonal structure and contain minority shares of intermetallic phase a2(Ti3AI) with hexagonal structure in addition to the majority phase y (TiAI) are particularly interesting. This y titanium aluminide alloys are characterized by properties like low density (3.85 - 4.2 g/cm3), high elastic modules, high rigidity and creep resistance up to 700 C, which make them attractive as a lightweight construction material for high-temperature applications. Examples of this are turbine buckets in aircraft engines and in stationary gas turbines, valves for engines and hot gas ventilators.
In the technically important area of alloys with aluminum content between 45 atom % and 49 atom %, a series of phase conversions occur during the solidification from the cast and during the subsequent cooling. The solidification can either take place completely via the (3 mixed crystal with a cubically body-centered structure (high temperature phase) or in two peritectic reactions, in which the a mixed crystal with hexagonal structure and the y phase participate.
Furthermore, it is known that aluminum in y titanium aluminide alloys causes an increase in the ductility and the oxidation resistance.
Moreover, element Niob (Nb) leads to an increase in the rigidity, creep resistance, oxidation resistance, but also the ductility. With the element boron, which is practically insoluble in the y phase, a grain refinement can be achieved in both the as-cast state and after the reshaping with subsequent heat treatment in the a area. An increased share of (3 phase in the structure as a result of low aluminum contents and high concentrations of (3 stabilizing elements can lead to rough dispersion of this phase and can cause deterioration of the mechanical properties.
The mechanical properties of titanium aluminide alloys are strongly anisotropic due to their deformation and breaking behavior but also due to the structural anisotropy of the preferably set lamellar structure or duplex structure. Casting processes, different powder-metall-urgical and reshaping processes and combinations of these production processes are used for a targeted setting of structure and texture in the production of components made of titanium aliminides.
Moreover, a titanium aluminide alloy, which has a structurally and chemically homogeneous structure, is known from EP 1 015 650 B1.
The majority phases y(TiAI) and a2 (Ti3AI) are hereby distributed in a finely disperse manner. The disclosed titanium aluminide alloy with an aluminum content of 45 atom % is characterized by extraordinarily good mechanical properties and high temperature properties.
Titanium aluminides based on y(TiAl) are characterized in general by relatively high rigidities, high elastic modules, good oxidation and creep resistance with simultaneously lower density. Based on these properties, TiAI alloys should be used as high temperature materials.
These types of applications are heavily impaired through the very low plastic malleability and the low fracture toughness. Rigidity and malleability, as with many other materials, behave hereby inversely.
The technically interesting high-strength alloys are thereby often particularly brittle. Comprehensive examinations for the optimization of the structure were performed in order to eliminate these disadvantageous properties.
The previously developed structure types can be roughly categorized into a) coaxial gamma structures, b) duplex structures and c) lamellar structures. The currently achieved development state is represented in detail for example in:
= Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, C.T. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, pg.
531.
= M. Yamaguchi, H. lnui, K. Ito, Acta mater. 48 (2000), pg. 307.
s The structures made of titanium aluminides were previously mainly refined by boron additives, which leads to the formation titanium borides (see T.T. Cheng in: Gamma Titanium Aluminides 1999, Eds.
Y.-W. Kim, D.M. Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999, pg. 389, and Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darolia, H.
Inui, J.M. Larsen, V.K. Sikka, M. Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001, pg. 625.) For further refining and consolidation of the structure, the alloys are usually subjected to several high temperature reshapings through extruding or forging. Also refer to the following publications:
= Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M.
Yamaguchi, TMS, Warrendale PA, 1995.
= Structurat Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, C.T. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997.
= Gamma Titanium Aluminides 1999, Eds. Y-W. Kim, D.M.
Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999.
= Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darotia, H. Inui, J.M. Larsen, V.K. Sikka, M.
Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001.
Proceeding from this state of the art, the object of the present invention is to make available a titanium aluminide alloy with a fine structure morphology, in particular in the nanometer range.
Furthermore, the object is to make available a component with a homogeneous alloy.
This object is solved through an intermetallic connection respectively an alloy based on titanium aluminides, in particular in particular made through the use of casting or powder metallurgical processes, preferably based on y(TiAI), in the following composition:
Ti - (38 to 42 atom %) Al - (5 to 10 atom %) Nb, wherein the composition comprises composite lamella structures with B19 phase and 0 phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the (3 phase in each lamella is between 0.05 and 20, in particular between 0.1 and 10.
It has been shown that in this type of intermetallic connection composite lamella structures with structures in the nanometer size are created respectively present, wherein the lamella-like formations respectively modulated lamellas are made of the crystallographically different, alternatingly formed B19 phase and (3 phase. The created composite lamella structures are hereby largely surrounded by y-TiAI.
These types of composite lamella structures can be established in alloys using known production technologies, i.e. through casting, reshaping and powder technologies. The ailoys are characterized by an extremely high rigidity and creep resistance with simultaneously high ductility and fracture toughness.
As additional (independent) and standalone solutions to this object, alloys are suggested, wherein an alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on y(TiAf), has one of the following compositions:
Ti-(38.5to42.5at%)AI-(5to 10at lo) Nb-(0.5to5at lo)Cr Ti-(39to43at lo)AI-(5to 10at%)Nb-(0.5to5at lo)Zr , Ti-(41to44.5at%)AI-(5to10at%)Nb-(0.5to5at%)Mo Ti-(41 to44.5 at lo)Al-(5to 10at%) Nb - (0.5 to 5 at %) Fe Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb - (0.1 to 1 at %) La Ti-(41 to45at%)Al-(5to 10at lo)Nb-(0.1 to 1 at%)Sc Ti-(41 to45at%)Al-(5to 10 at %) Nb - (0.1 to 1 at to)Y
Ti - (42 to 46 at %) Al - (5 to 10 at %) Nb - (0.5 to 5 at %) Mn Ti-(41 to 45 at %) Al - (5 to 10at /a)Nb-(0.5to5at%)Ta Ti-(41 to45at to)Al-(5to 10 at %) Nb - (0.5 to 5 at %) V 25 Ti-(41 to46at%)Al-(5to 10at%) Nb-(0.5to5 at lo)W.
Each of the named titanium aluminide alloys can optionally have the additives of boron and/or carbon, wherein in one embodiment the compositions of the named alloys respectively the intermetallic compounds each comprise optionally (0.1 to I at %) B (boron) and/or -7- , (0.1 to 1 at. %) C (carbon). The already fine structure of the alloy is hereby further refined.
Within the framework of the invention, the remainders of the specified alloy compositions are made of titanium and unavoidable impurities.
In accordance with the invention, alloys are thus made available, which are suitable as a lightweight construction material for high temperature applications, such as turbine buckets or engine and turbine components.
The alloys according to the invention are produced using casting metallurgical, casting metallurgical or powder metallurgical processes or techniques or using these processes in combination with reshaping techniques.
The alloys according to the invention are characterized in that they have a very fine microstructure and a high rigidity and creep resistance with simultaneously good ductility and fracture toughness, in particular with respect to alloys without the composite lamella structures according to the invention.
It is known that titanium aluminide alloys with aluminum contents of 38 - 45 at. % and other additives for example of refractory elements contain relatively large volume shares of the 0 phase, which can also be present in a controlled form as B2 phase. The crystallographic lattices of these two phases are mechanically instable with respect to homogenous shearing processes, which can lead to lattice conversions. This property is mainly attributed to the anistropic bond ratio and the symmetry of the cubically body-centered lattice. The tendency of the P or B2 phase towards lattice transformation is thus -~-very distinct. Different orthorhombic phases can be formed through a shear transformation of the cubically body-centered lattice of the (3 or B2 phase, to which phases B19 and B33 belong in particular.
The invention is based on the idea of using these lattice transformations through shear conversion for an additional refining of the microstructure of the titanium aluminide alloys according to the invention. This type of process is not previously known for titanium aluminide alloys in scientific literature. In the case of the alloys according to the invention listed above, brittle phases like co, co' and co " are also avoided through the shear conversions, which are extremely disadvantageous for the mechanical material properties.
An important advantage of the alloys according to the invention is that the structure refining of the alloys is achieved without the addition of grain-refining or structure-refining elements or additives such as boron (B) and the alloys thus contain no borides. Since the borides occurring in TiAI alloys are brittle, they lead to the brittleness of TiAI
alloys as of a certain content and generally represent potential crack nuclei in boron-containing alloys.
The alloys are further characterized in that the corresponding composition comprises composite lamella structures with the B19 phase and (3 phase in each lamella, wherein the lamellas are surrounded by the TiAI-y phase.
In particular, the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamelia is between 0.05 and 20, in particular between 0.1 and 10. Furthermore, the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamella is between 0.2 and 5, in particular between 0.25 and 4. Preferably, the ratio, in particular the volume ratio, of the B19 phase and P phase each in a lamella is between (1/3) and 3, in particular between 0.5 and 2. A
particularly fine structure in the alloy composition is also characterized in that the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamella is between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
Moreover, it is possible in a further embodiment of the alloys according to the invention that lamellas of the composite lamella structures are surrounded by lamellas of type y(TiAI), preferably on both sides of the lamella.
The alloys are further characterized in that the lamellas of the composite lamella structures have a volume share of more than 10%, preferably more than 20%, of the total alloy.
Moreover, the fine lamella-like structure in the composite structures are retained if the lamellas of the composite lamella structures TiAI
have the phase a2-Ti3Al with a share of up to 20%, wherein in particular the (volume) ratio of the B19 phase and (3 phase in the lamellas remains unchanged and constant.
The alloys according to the invention are suitable as high temperature lightweight construction material for components that are exposed to temperatures of up to 800 C.
The object is also solved through a method for the production of an alloy described above using casting or powder metallurgical techniques, wherein after the production of the alloy into an intermediate product another heat treatment of the intermediate -.10-.
product is performed at temperatures above 900 C, preferably above 1000 C, in particular at temperatures between 1000 C and 1200 C, for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes, and the heat-treated alloy is subsequently cooled with a predetermined cooling rate of more than 0.5 C per minute.
In particular, the heat-treated alloy is cooled with a predetermined cooling rate between 1 C per minute to 20 C per minute, preferably up to 10 C per minute.
The object of the invention is also solved through a component, which is made of an alloy according to the invention, wherein in particular the alloy is made through casting or powder metallurgical processes or techniques. Through the alloys based on an intermetallic bond of type y-TiAI, light (high temperature) materials or components are made available for use in thermal engines like combustion engines, gas turbines, aircraft engines.
The object is also solved in a use of an alloy according to the invention mentioned above for the production of a component. To avoid repetitions reference is made expressly to the above expositions.
The alloys according to the invention with the compositions listed above are preferably created through the use of conventional metallurgical casting methods or through known powder metallurgical techniques and can for example be processed through hot forging, hot pressing or hot extrusion and hot rolling.
The composite lamella structures are shown below based on an alloy according to the invention with a composition Ti - 42 atom % Al - 8.5 atom % Nb.
Fig. 1 a shows a picture of a structure alloy, which was taken with the help of a transmission electron microscope. The overview picture in Fig. 1 shows that the composite lamella structures, which are labeled with T in Fig. 1, have a striped contrast to the structure of the y phase surrounding the structures.
Fig. lb shows a picture of the alloy structure with a higher magnification, whereby it can be seen that the modulated composite lamella structures (reference letter T) are surrounded by the y phase respectively are embedded in the y phase.
The structures shown in Fig. 1 a and 1 b were obtained or set through extrusion.
Fig. 1c shows a cast structure of the same alloy Ti-42 atom % Al-8.5 atom % Nb, in which a composite lamella structure (reference letter T) is also formed, which is surrounding by the y phase.
Fig. 2a shows a high resolution illustration of the atomic structure of the composite lamella structures above the y phase. The composite lamella structures are made up of the controlled B19 phase and the uncontrolled 0 phase, which border the y phase (in the lower area). It can be seen from the picture in Fig. 2a that the composite lamella structures contain the two crystallographically different phases B19 and (i/B2, which are arranged at separation distances of a few nanometers. The composite lamella structures contain the phases B19 and P, which are both considered ductile. The volume ratio of the B19 phases and the (3 phases in a composite lamella structure is 0.8 to 1.2. Due to the ductile phases B19 and (3, the structure is mainly made of easily malleable lamellas, which are embedded in the previously relatively brittle y phase.
Fig. 2b shows an illustration of a B19 structure with a magnified representation. The corresponding diffractogram, which was calculated from the section shown in Fig. 2b and is characteristic for the B19 structure, is shown in Fig. 2c.
Fig. 3 shows an electron-microscopic picture of a crack C in the aforementioned alloy. It can be seen from the picture that the crack C
is diffracted at the modulated composite lamella structures (T) and that the composite lamella structures form ligaments that can bridge the edge of the crack. This type of behavior is considerably different from the crack propagation in the previously known Ti-Al alloys, in which a cleavage fracture occurs in the microscopic dimension observed here. In the alloy according to the invention, crack propagation is prevented due to the formed composite lamella structures.
The fracture toughness of structure important for the technical application was determined with the help of notched Chevron samples in the bending test at different temperatures. The recorded register curve of such a test is shown in Fig. 4. The indentations marked by the arrows can be seen in the curve, which indicate that crack propagation intermittently occurs during the loading of the sample, but is stopped again and again. Such a behavior is typical for alloys that are made up of a brittle phase (y phase), in which the relative ductile phases B19 and (3 are embedded.
The alloys according to the invention can be made through the technologies known for TiAI alloys, i.e. via casting metallurgy, reshaping technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and are re-melted multiple times and are then underwent a heat treatment. Moreover, the production methods of vacuum arc casting, induction casting or plasma casting, which are known for primary cast blocks made of TiAI alloys, can be used for production. After the solidification of casting primary cast material, hot-isostatic presses can also be used as the compression method at temperatures of 900 C to 1,300 C or heat treatments in the temperature range of 700 C to 1,4000 C or a combination of these treatments, in order to close pores and to establish a microstructure in the material.
= M. Yamaguchi, H. lnui, K. Ito, Acta mater. 48 (2000), pg. 307.
s The structures made of titanium aluminides were previously mainly refined by boron additives, which leads to the formation titanium borides (see T.T. Cheng in: Gamma Titanium Aluminides 1999, Eds.
Y.-W. Kim, D.M. Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999, pg. 389, and Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darolia, H.
Inui, J.M. Larsen, V.K. Sikka, M. Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001, pg. 625.) For further refining and consolidation of the structure, the alloys are usually subjected to several high temperature reshapings through extruding or forging. Also refer to the following publications:
= Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M.
Yamaguchi, TMS, Warrendale PA, 1995.
= Structurat Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, C.T. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997.
= Gamma Titanium Aluminides 1999, Eds. Y-W. Kim, D.M.
Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999.
= Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darotia, H. Inui, J.M. Larsen, V.K. Sikka, M.
Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001.
Proceeding from this state of the art, the object of the present invention is to make available a titanium aluminide alloy with a fine structure morphology, in particular in the nanometer range.
Furthermore, the object is to make available a component with a homogeneous alloy.
This object is solved through an intermetallic connection respectively an alloy based on titanium aluminides, in particular in particular made through the use of casting or powder metallurgical processes, preferably based on y(TiAI), in the following composition:
Ti - (38 to 42 atom %) Al - (5 to 10 atom %) Nb, wherein the composition comprises composite lamella structures with B19 phase and 0 phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the (3 phase in each lamella is between 0.05 and 20, in particular between 0.1 and 10.
It has been shown that in this type of intermetallic connection composite lamella structures with structures in the nanometer size are created respectively present, wherein the lamella-like formations respectively modulated lamellas are made of the crystallographically different, alternatingly formed B19 phase and (3 phase. The created composite lamella structures are hereby largely surrounded by y-TiAI.
These types of composite lamella structures can be established in alloys using known production technologies, i.e. through casting, reshaping and powder technologies. The ailoys are characterized by an extremely high rigidity and creep resistance with simultaneously high ductility and fracture toughness.
As additional (independent) and standalone solutions to this object, alloys are suggested, wherein an alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on y(TiAf), has one of the following compositions:
Ti-(38.5to42.5at%)AI-(5to 10at lo) Nb-(0.5to5at lo)Cr Ti-(39to43at lo)AI-(5to 10at%)Nb-(0.5to5at lo)Zr , Ti-(41to44.5at%)AI-(5to10at%)Nb-(0.5to5at%)Mo Ti-(41 to44.5 at lo)Al-(5to 10at%) Nb - (0.5 to 5 at %) Fe Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb - (0.1 to 1 at %) La Ti-(41 to45at%)Al-(5to 10at lo)Nb-(0.1 to 1 at%)Sc Ti-(41 to45at%)Al-(5to 10 at %) Nb - (0.1 to 1 at to)Y
Ti - (42 to 46 at %) Al - (5 to 10 at %) Nb - (0.5 to 5 at %) Mn Ti-(41 to 45 at %) Al - (5 to 10at /a)Nb-(0.5to5at%)Ta Ti-(41 to45at to)Al-(5to 10 at %) Nb - (0.5 to 5 at %) V 25 Ti-(41 to46at%)Al-(5to 10at%) Nb-(0.5to5 at lo)W.
Each of the named titanium aluminide alloys can optionally have the additives of boron and/or carbon, wherein in one embodiment the compositions of the named alloys respectively the intermetallic compounds each comprise optionally (0.1 to I at %) B (boron) and/or -7- , (0.1 to 1 at. %) C (carbon). The already fine structure of the alloy is hereby further refined.
Within the framework of the invention, the remainders of the specified alloy compositions are made of titanium and unavoidable impurities.
In accordance with the invention, alloys are thus made available, which are suitable as a lightweight construction material for high temperature applications, such as turbine buckets or engine and turbine components.
The alloys according to the invention are produced using casting metallurgical, casting metallurgical or powder metallurgical processes or techniques or using these processes in combination with reshaping techniques.
The alloys according to the invention are characterized in that they have a very fine microstructure and a high rigidity and creep resistance with simultaneously good ductility and fracture toughness, in particular with respect to alloys without the composite lamella structures according to the invention.
It is known that titanium aluminide alloys with aluminum contents of 38 - 45 at. % and other additives for example of refractory elements contain relatively large volume shares of the 0 phase, which can also be present in a controlled form as B2 phase. The crystallographic lattices of these two phases are mechanically instable with respect to homogenous shearing processes, which can lead to lattice conversions. This property is mainly attributed to the anistropic bond ratio and the symmetry of the cubically body-centered lattice. The tendency of the P or B2 phase towards lattice transformation is thus -~-very distinct. Different orthorhombic phases can be formed through a shear transformation of the cubically body-centered lattice of the (3 or B2 phase, to which phases B19 and B33 belong in particular.
The invention is based on the idea of using these lattice transformations through shear conversion for an additional refining of the microstructure of the titanium aluminide alloys according to the invention. This type of process is not previously known for titanium aluminide alloys in scientific literature. In the case of the alloys according to the invention listed above, brittle phases like co, co' and co " are also avoided through the shear conversions, which are extremely disadvantageous for the mechanical material properties.
An important advantage of the alloys according to the invention is that the structure refining of the alloys is achieved without the addition of grain-refining or structure-refining elements or additives such as boron (B) and the alloys thus contain no borides. Since the borides occurring in TiAI alloys are brittle, they lead to the brittleness of TiAI
alloys as of a certain content and generally represent potential crack nuclei in boron-containing alloys.
The alloys are further characterized in that the corresponding composition comprises composite lamella structures with the B19 phase and (3 phase in each lamella, wherein the lamellas are surrounded by the TiAI-y phase.
In particular, the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamelia is between 0.05 and 20, in particular between 0.1 and 10. Furthermore, the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamella is between 0.2 and 5, in particular between 0.25 and 4. Preferably, the ratio, in particular the volume ratio, of the B19 phase and P phase each in a lamella is between (1/3) and 3, in particular between 0.5 and 2. A
particularly fine structure in the alloy composition is also characterized in that the ratio, in particular the volume ratio, of the B19 phase and (3 phase each in a lamella is between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
Moreover, it is possible in a further embodiment of the alloys according to the invention that lamellas of the composite lamella structures are surrounded by lamellas of type y(TiAI), preferably on both sides of the lamella.
The alloys are further characterized in that the lamellas of the composite lamella structures have a volume share of more than 10%, preferably more than 20%, of the total alloy.
Moreover, the fine lamella-like structure in the composite structures are retained if the lamellas of the composite lamella structures TiAI
have the phase a2-Ti3Al with a share of up to 20%, wherein in particular the (volume) ratio of the B19 phase and (3 phase in the lamellas remains unchanged and constant.
The alloys according to the invention are suitable as high temperature lightweight construction material for components that are exposed to temperatures of up to 800 C.
The object is also solved through a method for the production of an alloy described above using casting or powder metallurgical techniques, wherein after the production of the alloy into an intermediate product another heat treatment of the intermediate -.10-.
product is performed at temperatures above 900 C, preferably above 1000 C, in particular at temperatures between 1000 C and 1200 C, for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes, and the heat-treated alloy is subsequently cooled with a predetermined cooling rate of more than 0.5 C per minute.
In particular, the heat-treated alloy is cooled with a predetermined cooling rate between 1 C per minute to 20 C per minute, preferably up to 10 C per minute.
The object of the invention is also solved through a component, which is made of an alloy according to the invention, wherein in particular the alloy is made through casting or powder metallurgical processes or techniques. Through the alloys based on an intermetallic bond of type y-TiAI, light (high temperature) materials or components are made available for use in thermal engines like combustion engines, gas turbines, aircraft engines.
The object is also solved in a use of an alloy according to the invention mentioned above for the production of a component. To avoid repetitions reference is made expressly to the above expositions.
The alloys according to the invention with the compositions listed above are preferably created through the use of conventional metallurgical casting methods or through known powder metallurgical techniques and can for example be processed through hot forging, hot pressing or hot extrusion and hot rolling.
The composite lamella structures are shown below based on an alloy according to the invention with a composition Ti - 42 atom % Al - 8.5 atom % Nb.
Fig. 1 a shows a picture of a structure alloy, which was taken with the help of a transmission electron microscope. The overview picture in Fig. 1 shows that the composite lamella structures, which are labeled with T in Fig. 1, have a striped contrast to the structure of the y phase surrounding the structures.
Fig. lb shows a picture of the alloy structure with a higher magnification, whereby it can be seen that the modulated composite lamella structures (reference letter T) are surrounded by the y phase respectively are embedded in the y phase.
The structures shown in Fig. 1 a and 1 b were obtained or set through extrusion.
Fig. 1c shows a cast structure of the same alloy Ti-42 atom % Al-8.5 atom % Nb, in which a composite lamella structure (reference letter T) is also formed, which is surrounding by the y phase.
Fig. 2a shows a high resolution illustration of the atomic structure of the composite lamella structures above the y phase. The composite lamella structures are made up of the controlled B19 phase and the uncontrolled 0 phase, which border the y phase (in the lower area). It can be seen from the picture in Fig. 2a that the composite lamella structures contain the two crystallographically different phases B19 and (i/B2, which are arranged at separation distances of a few nanometers. The composite lamella structures contain the phases B19 and P, which are both considered ductile. The volume ratio of the B19 phases and the (3 phases in a composite lamella structure is 0.8 to 1.2. Due to the ductile phases B19 and (3, the structure is mainly made of easily malleable lamellas, which are embedded in the previously relatively brittle y phase.
Fig. 2b shows an illustration of a B19 structure with a magnified representation. The corresponding diffractogram, which was calculated from the section shown in Fig. 2b and is characteristic for the B19 structure, is shown in Fig. 2c.
Fig. 3 shows an electron-microscopic picture of a crack C in the aforementioned alloy. It can be seen from the picture that the crack C
is diffracted at the modulated composite lamella structures (T) and that the composite lamella structures form ligaments that can bridge the edge of the crack. This type of behavior is considerably different from the crack propagation in the previously known Ti-Al alloys, in which a cleavage fracture occurs in the microscopic dimension observed here. In the alloy according to the invention, crack propagation is prevented due to the formed composite lamella structures.
The fracture toughness of structure important for the technical application was determined with the help of notched Chevron samples in the bending test at different temperatures. The recorded register curve of such a test is shown in Fig. 4. The indentations marked by the arrows can be seen in the curve, which indicate that crack propagation intermittently occurs during the loading of the sample, but is stopped again and again. Such a behavior is typical for alloys that are made up of a brittle phase (y phase), in which the relative ductile phases B19 and (3 are embedded.
The alloys according to the invention can be made through the technologies known for TiAI alloys, i.e. via casting metallurgy, reshaping technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and are re-melted multiple times and are then underwent a heat treatment. Moreover, the production methods of vacuum arc casting, induction casting or plasma casting, which are known for primary cast blocks made of TiAI alloys, can be used for production. After the solidification of casting primary cast material, hot-isostatic presses can also be used as the compression method at temperatures of 900 C to 1,300 C or heat treatments in the temperature range of 700 C to 1,4000 C or a combination of these treatments, in order to close pores and to establish a microstructure in the material.
Claims (25)
1. An alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti - (38 to 42 atom %) Al - (5 to 10 atom %) Nb, wherein the composition comprises composite lamella structures with B19 phase and .beta. phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the .beta. phase in each lamella is between 0.05 and 20, in particular between 0.1 and 10.
Ti - (38 to 42 atom %) Al - (5 to 10 atom %) Nb, wherein the composition comprises composite lamella structures with B19 phase and .beta. phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the .beta. phase in each lamella is between 0.05 and 20, in particular between 0.1 and 10.
2. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti - (38.5 to 42.5 at %) Al - (5 to 10 at %) Nb-(0.5 to 5 at %)Cr.
Ti - (38.5 to 42.5 at %) Al - (5 to 10 at %) Nb-(0.5 to 5 at %)Cr.
3. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(39 to 43 at %)Al-(5 to 10 at %)Nb-(0.5 to 5 at %)Zr.
Ti-(39 to 43 at %)Al-(5 to 10 at %)Nb-(0.5 to 5 at %)Zr.
4. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. TiAl), in the following composition:
Ti-(41 to 44.5 at %) Al - (5 to 10 at %) Nb - (0.5 to 5 at %) Mo.
Ti-(41 to 44.5 at %) Al - (5 to 10 at %) Nb - (0.5 to 5 at %) Mo.
5. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(41 to 44.5 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) Fe.
Ti-(41 to 44.5 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) Fe.
6. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb - (0.1 to 1 at %) La.
Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb - (0.1 to 1 at %) La.
7. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb -(0.1 to 1 at %) Sc.
Ti - (41 to 45 at %) Al - (5 to 10 at %) Nb -(0.1 to 1 at %) Sc.
8. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(41 to 45 at %)Al -(5 to 10 at %) Nb-(0.1 to 1 at %)Y.
Ti-(41 to 45 at %)Al -(5 to 10 at %) Nb-(0.1 to 1 at %)Y.
9. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(42 to 46 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) Mn.
Ti-(42 to 46 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) Mn.
10. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma.(TiAl), in the following composition:
Ti-(41 to 45 at %)Al -(5 to 10 at %)Nb-(0.5 to 5 at %)Ta.
Ti-(41 to 45 at %)Al -(5 to 10 at %)Nb-(0.5 to 5 at %)Ta.
11. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(41 to 45 at %)Al -(5 to 10 at %)Nb-(0.5 to 5 at %)V.
Ti-(41 to 45 at %)Al -(5 to 10 at %)Nb-(0.5 to 5 at %)V.
12. An Alloy based on titanium aluminides, in particular made through the use of casting or powder metallurgical processes, preferably based on .gamma. (TiAl), in the following composition:
Ti-(41 to 46 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) W.
Ti-(41 to 46 at %)Al -(5 to 10 at %) Nb - (0.5 to 5 at %) W.
13. An Alloy according to one of claims 1 through 12, characterized in that the composition optionally comprises (0.1 to 1 at. %) B (boron) and/or (0.1 to 1 at. %) C (carbon).
14. An Alloy according to one of claims 2 through 12, characterized in that the composition comprises composite lamella structures with B19 phase and .beta. phase in each lamella.
15. An Alloy according to claim 1 or 14, characterized in that the ratio, in particular the volume ratio, of the B19 phase and .beta. phase each in a lamella is between 0.05 and 20, in particular between 0.1 and 10.
16. An Alloy according to claim 1 or 15, characterized in that the ratio, in particular the volume ratio, of the B19 phase and .beta. phase each in a lamella is between 0.2 and 5, in particular between 0.25 and 4.
17. An Alloy according to claim 1 or 16, characterized in that the ratio, in particular the volume ratio, of the B19 phase and .beta. phase each in a lamella is between (1/3) and 3, in particular between 0.5 and 2.
18. An Alloy according to claim 1 or 17, characterized in that the ratio, in particular the volume ratio, of the B19 phase and .beta. phase each in a lamella is between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
19. An Alloy according to one of claim 1 through 18, characterized in that lamellas of the composite lamella structures are surrounded by lamellas of type .gamma. (TiAl), preferably on both sides of the lamella.
20. An Alloy according to one of claims 1 through 19, characterized in that lamellas of the composite lamella structures have a volume share of more than 10%, preferably more than 20%, of the alloy.
21. An Alloy according to one of claims 1 through 20, characterized in that the lamellas of the composite lamella structures have the phase .alpha.2-Ti3Al with a share of up to 20%.
22. A method for the production of an alloy according to one of claims 1 through 22 using casting or powder metallurgical techniques, wherein after the production of the alloy into an intermediate product another heat treatment of the intermediate product is performed at temperatures above 900° C, preferably above 1000° C, in particular at temperatures between 1000° C and 1200° C, for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes, and the heat-treated alloy is subsequently cooled with a predetermined cooling rate of more than 0.5° C per minute.
23. A method according to claim 22, characterized in that the heat-treated alloy is cooled with a predetermined cooling rate between 1° C per minute to 20° C per minute, preferably up to 10° C
per minute.
per minute.
24. A component, which is made of an alloy according to one of claims 1 through 21, wherein in particular the alloy is produced through casting or powder metallurgical processes or techniques.
25. A use of an alloy according to one of claims 1 through 21 for the production of a component.
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|---|---|---|---|
| DE102007060587.2 | 2007-12-13 | ||
| DE102007060587A DE102007060587B4 (en) | 2007-12-13 | 2007-12-13 | titanium aluminide |
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| CA2645843A1 true CA2645843A1 (en) | 2009-06-13 |
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| CA002645843A Abandoned CA2645843A1 (en) | 2007-12-13 | 2008-12-04 | Titanium aluminide alloys |
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| US (3) | US20090151822A1 (en) |
| EP (3) | EP2075349B1 (en) |
| JP (1) | JP5512964B2 (en) |
| KR (1) | KR20090063173A (en) |
| CN (1) | CN101457314B (en) |
| BR (1) | BRPI0806979A2 (en) |
| CA (1) | CA2645843A1 (en) |
| DE (1) | DE102007060587B4 (en) |
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| US5558729A (en) * | 1995-01-27 | 1996-09-24 | The United States Of America As Represented By The Secretary Of The Air Force | Method to produce gamma titanium aluminide articles having improved properties |
| JPH1161298A (en) * | 1997-08-18 | 1999-03-05 | Natl Res Inst For Metals | Titanium-aluminum intermetallic compound-base alloy and its production |
| DE19735841A1 (en) * | 1997-08-19 | 1999-02-25 | Geesthacht Gkss Forschung | Titanium aluminide alloy contains niobium |
| US6174387B1 (en) * | 1998-09-14 | 2001-01-16 | Alliedsignal, Inc. | Creep resistant gamma titanium aluminide alloy |
| JP2000199025A (en) * | 1999-01-05 | 2000-07-18 | Mitsubishi Heavy Ind Ltd | TiAl INTERMETALLIC COMPOUND BASE ALLOY, ITS PRODUCTION, TURBINE MEMBER AND ITS PRODUCTION |
| DE10351946A1 (en) * | 2003-03-21 | 2004-10-07 | Dechema Gesellschaft Für Chemische Technik Und Biotechnologie E.V. | Process for treating the surface of a component consisting of an AL alloy, in particular a TiAL alloy, and the use of organic halocarbon compounds or halides incorporated in an organic matrix |
| DE102004056582B4 (en) * | 2004-11-23 | 2008-06-26 | Gkss-Forschungszentrum Geesthacht Gmbh | Alloy based on titanium aluminides |
| GB0616566D0 (en) * | 2006-08-19 | 2006-09-27 | Rolls Royce Plc | An alloy and method of treating titanium aluminide |
| CN101011705A (en) * | 2007-01-31 | 2007-08-08 | 哈尔滨工业大学 | Method for preparation of Yt-containing TiAl intermetallic compound plate material |
-
2007
- 2007-12-13 DE DE102007060587A patent/DE102007060587B4/en not_active Expired - Fee Related
-
2008
- 2008-11-25 EP EP08020431.6A patent/EP2075349B1/en not_active Not-in-force
- 2008-11-25 EP EP11187502.7A patent/EP2423341B1/en not_active Not-in-force
- 2008-11-25 EP EP09010152.8A patent/EP2145967B1/en not_active Not-in-force
- 2008-12-04 CA CA002645843A patent/CA2645843A1/en not_active Abandoned
- 2008-12-07 IL IL195756A patent/IL195756A0/en unknown
- 2008-12-10 US US12/331,909 patent/US20090151822A1/en not_active Abandoned
- 2008-12-11 BR BRPI0806979-4A patent/BRPI0806979A2/en not_active IP Right Cessation
- 2008-12-12 CN CN2008101727696A patent/CN101457314B/en not_active Expired - Fee Related
- 2008-12-12 KR KR1020080126803A patent/KR20090063173A/en not_active Application Discontinuation
- 2008-12-12 RU RU2008149177/02A patent/RU2466201C2/en not_active IP Right Cessation
- 2008-12-15 JP JP2008318555A patent/JP5512964B2/en active Active
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2009
- 2009-07-30 US US12/512,451 patent/US20100000635A1/en not_active Abandoned
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2013
- 2013-06-28 US US13/931,051 patent/US20140010701A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| RU2008149177A (en) | 2010-06-20 |
| RU2466201C2 (en) | 2012-11-10 |
| EP2145967A2 (en) | 2010-01-20 |
| BRPI0806979A2 (en) | 2010-04-20 |
| US20140010701A1 (en) | 2014-01-09 |
| JP2009144247A (en) | 2009-07-02 |
| US20090151822A1 (en) | 2009-06-18 |
| EP2075349A2 (en) | 2009-07-01 |
| EP2423341A1 (en) | 2012-02-29 |
| EP2145967B1 (en) | 2013-07-24 |
| EP2423341B1 (en) | 2013-07-10 |
| CN101457314B (en) | 2013-07-24 |
| EP2075349A3 (en) | 2009-09-09 |
| DE102007060587B4 (en) | 2013-01-31 |
| JP5512964B2 (en) | 2014-06-04 |
| EP2075349B1 (en) | 2016-03-09 |
| US20100000635A1 (en) | 2010-01-07 |
| EP2145967A3 (en) | 2010-04-21 |
| IL195756A0 (en) | 2009-11-18 |
| CN101457314A (en) | 2009-06-17 |
| DE102007060587A1 (en) | 2009-06-18 |
| KR20090063173A (en) | 2009-06-17 |
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| FZDE | Discontinued |
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