[go: up one dir, main page]

EP2995695B1 - Method for processing titanium aluminide intermetallic compositions - Google Patents

Method for processing titanium aluminide intermetallic compositions Download PDF

Info

Publication number
EP2995695B1
EP2995695B1 EP15184357.0A EP15184357A EP2995695B1 EP 2995695 B1 EP2995695 B1 EP 2995695B1 EP 15184357 A EP15184357 A EP 15184357A EP 2995695 B1 EP2995695 B1 EP 2995695B1
Authority
EP
European Patent Office
Prior art keywords
titanium aluminide
casting
tial
aluminide intermetallic
composition
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.)
Active
Application number
EP15184357.0A
Other languages
German (de)
French (fr)
Other versions
EP2995695A1 (en
Inventor
Thomas Joseph Kelly
Bernard Patrick BEWLEY
Michael James Weimer
Richard Kenneth Whitacre
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=47913098&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2995695(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP2995695A1 publication Critical patent/EP2995695A1/en
Application granted granted Critical
Publication of EP2995695B1 publication Critical patent/EP2995695B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the present invention generally relates to compositions containing titanium and aluminum and the processing thereof. More particularly, this invention relates to methods of processing cast titanium aluminide intermetallic compositions that entail hot isostatic pressing and heat treatment to close porosity and yield a desirable microstructure.
  • Titanium-based alloy systems are well known in the art as having mechanical properties that are suitable for relatively high temperature applications.
  • High temperature capabilities of titanium-based alloys has increased through the use of titanium intermetallic systems based on the titanium aluminide compounds Ti 3 Al (alpha-2 ( ⁇ -2) alloys) and TiAl (gamma (y) alloys).
  • These titanium aluminide intermetallic compounds are generally characterized as being relatively light weight, yet are known to be capable of exhibiting high strength, creep strength and fatigue resistance at elevated temperatures.
  • Additions of chromium and niobium are known to promote certain properties of TiAl intermetallics, such as oxidation resistance, ductility, strength, etc.
  • U.S. Patent No. 4,879,092 to Huang discloses a titanium aluminide intermetallic composition having an approximate formula of Ti 46-50 Al 46-50 Cr 2 Nb 2 , or nominally about Ti-48Al-2Cr-2Nb.
  • This alloy, referred to herein as the 48-2-2 alloy is considered to have a nominal temperature capability of up to about 1400°F (about 760°C), with useful but diminishing capabilities up to about 1500°F (about 815°C).
  • the 48-2-2 alloy is well suited for low pressure turbine blade (LPTB) applications.
  • Hot isostatic pressing is commonly performed to eliminate internal voids and microporosity in titanium aluminide intermetallic castings. Because uncontrolled cooling rates typically performed following HIP are not effective to generate a desired microstructure, responsiveness to post-HIP heat treatments is another desirable characteristic in order to achieve microstructures and mechanical properties needed for specific applications.
  • US 6,231,699 B1 relates to a process for heat treatment of gamma titanim aluminide alloy articles.
  • HIP cycles are typically separate from the heat treatment cycle in the processing of castings.
  • desired microstructures and mechanical properties have been obtained in castings of the 48-2-2 alloy using a process represented in FIG. 3 .
  • a pre-HIP heat treatment is performed at a temperature within a range of about 1800 to about 2000°F (about 980 to about 1090°C) and for a duration of about five to twelve hours.
  • the casting is cooled and transferred to a HIP chamber and then subjected to a high pressure HIP step (for example, 25 ksi (about 1720 bar) or more) at about 2165°F for a duration of about three hours.
  • a high pressure HIP step for example, 25 ksi (about 1720 bar) or more
  • the HIPed casting is then cooled, removed from the HIP chamber, and then subjected to a post-HIP solution treatment at a temperature of about 2200°F for a duration of about two hours.
  • This sequence requires the use of at least two different vessels and loading and unloading the casting three times from these vessels. In addition to incurring additional cost and cycle time, this process has been associated with the loss of aluminum from the casting surface, which leads to reduced environmental and/or mechanical properties.
  • FIGS. 1 and 2 are photomicrographs showing desirable duplex microstructures present in two conventional TiAl castings.
  • a method is needed that is capable of processing TiAl intermetallics, including but not limited to net-shape geometries of the 48-2-2 alloy, to yield a duplex microstructure containing equiaxed and lamellar morphologies. It would be further desirable if such a method did not require a sequence in which a casting is not required to be transferred between multiple different vessels.
  • the present invention provides methods capable of processing compositions containing titanium and aluminum, and especially titanium aluminide intermetallic compositions (TiAl intermetallics) based on the TiAl (gamma) intermetallic compound, to yield desirable microstructures.
  • the methods have the further capability of being performed in a single vessel, resulting in a less complicated process than conventional methods used to produce compositions that require void closure (for example, by HIPing) and heat treatment.
  • a method of processing a titanium aluminide intermetallic composition includes hot isostatic pressing the titanium aluminide intermetallic composition, cooling the composition, heat treating the composition at a temperature of at least 1260°C (about 2300°F) for 2.5 to 5 hours, cooling the composition to a temperature of not less than 1150°C (2100°F), holding the composition at a hold temperature of 1150 to 1200°C (2100 to 2200°F) for a duration of two to six hours, and then cooling the composition to room temperature.
  • the titanium aluminide intermetallic composition exhibits a desirable duplex microstructure containing equiaxed and lamellar morphologies of the gamma TiAl phase.
  • a beneficial effect of the invention is the ability to produce desirable duplex microstructures in TiAl intermetallics that may otherwise be difficult to obtain, particularly if produced by net-shape casting methods such as spin casting and possibly certain other casting techniques.
  • Another beneficial effect is the ability to take advantage of the energy available for phase equilibration during cool down from a HIP step to assist in a subsequent heat treatment, which has been determined to eliminate the requirement for conventional pre- and post-heat treatment cycles that may cause aluminum to be lost from the casting surface as well as incur additional cost and cycle time.
  • FIGS. 4 and 5 contain flow charts that represent two related methods by which TiAl intermetallic compositions, including but not limited to the 48-2-2 alloy, can be processed to yield a desirable duplex microstructure, with the additional benefit of avoiding the disadvantages of the prior art process summarized in FIG. 3 .
  • the methods of FIGS. 4 and 5 avoid the pre- and post-HIP vacuum heat treatments that are believed to promote the loss of aluminum in TiAl intermetallic compositions.
  • the invention also takes advantage of the high gas pressures and protective (inert) atmospheres used during HIP, the combination of which is believed to be capable of reducing the loss of aluminum in a TiAl intermetallic composition.
  • FIG. 4 and 5 provide for interrupted cooling from a HIP step ( FIG. 4 ) or a temperature that is believed to take advantage of the non-equilibrium phase distribution in TiAl intermetallic compositions following HIP ( FIG. 5 ) to generate (during a subsequent heat treatment) microstructures that are capable of providing desirable mechanical properties, especially if the TiAl intermetallic composition is a cast using a net-shape casting process, such as spin casting or other means.
  • FIGS. 4 and 5 are believed to be particularly beneficial to the 48-2-2 alloy, whose composition is based on the gamma (TiAl) intermetallic compound. Castings of the 48-2-2 alloy exhibit improved ductility and other desirable properties if they contain a duplex microstructure containing equiaxed and lamellar gamma phase morphologies.
  • FIGS. 6 and 7 are representative of LPTB castings produced from the 48-2-2 alloy. Both castings were produced by spin casting, the casting in FIG. 6 was processed by a HIP and heat treatment procedure corresponding to that represented in FIG. 3 , and the casting in FIG. 7 was processed by a modified HIP and heat treatment procedure corresponding to that represented in FIG. 4 .
  • the microstructure of the heat treated casting shown in FIG. 6 possesses an excessive amount of equiaxed gamma phase and an inadequate amount of the lamellar phase (less than 10% volume fraction of the lamellar phase). Such a microstructure would yield a component with insufficiently high temperature creep strength.
  • the microstructure of the heat treated casting shown in FIG. 7 has acceptable amounts of the equiaxed gamma phase and the lamellar phase (about 20% volume fraction of the lamellar phase), the sole exception being at the outermost surface of the casting where titanium levels are depleted. However, the outermost surface can be removed by conventional techniques, such as abrasive blasting or chemical milling, with the result that the entire remaining casting would contain acceptable amounts of the equiaxed gamma phase and lamellar phase.
  • the invention has been shown to yield particularly advantageous results with the 48-2-2 alloy, the invention is believed to be more generally applicable to titanium aluminide intermetallic compositions, particularly TiAl (gamma) intermetallic compositions modified with elements that are intended to promote various properties.
  • the invention has also been shown to be effective with TiAl intermetallic compositions that contain tantalum.
  • Particular compositions that have been successfully evaluated include TiAl compositions that contain chromium, niobium and/or tantalum, for example, about 1.8 to about 2 atomic percent chromium, up to about 2 atomic percent niobium, and up to about 4 atomic percent tantalum.
  • compositions that were successfully evaluated contained, in atomic percent: about 47.3% aluminum, about 1.9% chromium, about 1.9% niobium and the balance titanium and incidental impurities (roughly corresponding to the 48-2-2 alloy); or about 47.3% aluminum, about 1.8% chromium, about 0.85% niobium, about 1.7% tantalum and the balance titanium and incidental impurities; or about 47.3% aluminum, about 2.0% chromium, about 4.0% tantalum and the balance titanium and incidental impurities. More generally, the levels of titanium and aluminum in these TiAl intermetallic compositions are selected to yield a casting whose predominant constituent is the TiAl (gamma) intermetallic compound.
  • compositions evaluated all contained about 47.3 atomic percent aluminum and about 46.7 to 48.9 atomic percent titanium, those skilled in the art will appreciate that aluminum and titanium levels beyond these amounts can be used to yield a casting that is entirely or predominantly the TiAl intermetallic compound, and such variations are within the scope of the invention. Furthermore, those skilled in the art will recognize that other alloy constituents could be included to modify the properties of the TiAl intermetallic compound, and such variations are also within the scope of the invention.
  • the process of FIG. 4 generally entails preparing a TiAl intermetallic composition.
  • a preferred but not limiting example entails spin casting an appropriate melt containing the desired constituents of the TiAl intermetallic composition.
  • the composition (casting) is then loaded in a suitable HIP chamber and heated in a protective atmosphere (for example, argon or another inert gas) to a temperature at which the casting is to undergo HIPing.
  • the HIP temperature (T HIPI) is at least 2300°F (about 1260°C), more preferably at least 2350°F (about 1290°C), and most preferably in a range of 2375 to 2425°F (about 1300 to about 1330°C).
  • the pressure applied to the casting during the HIP cycle is intended to eliminate internal voids and microporosity in the castings.
  • pressures of at least 15 ksi (about 1030 bar) are believed to be sufficient, with pressures of about 18 ksi (about 1240 bar) and higher believed to be particularly preferred.
  • the duration of the HIP cycle may vary depending on the particular composition and pressure used, but suitable results are believed to be obtained with HIP cycles having durations of 2.5 to 5 hours, and particularly 2.5 to 3.5 hours.
  • the casting is cooled to a temperature of not less than 2100°F (1150°C), and most preferably 2100 to 2150°F (1150 to 1175°C).
  • the cooling rate may vary, but rates of about 5 to about 20°F/minute (about 3 to about 11 °C/minute) have been found to be acceptable.
  • the casting then undergoes a heat treatment at a temperature of about 2100 to about 2200°F (about 1150 to about 1200°C), for example, about 2100 to about 2150°F (about 1150 to about 1175°C).
  • the duration of this heat treatment may vary depending on the particular composition and HIP treatment used, but suitable results are believe to be obtained with heat treatment cycles having durations of about two to about six hours, and especially about 4.5 to about 5.5 hours.
  • the casting can be cooled directly to room temperature (about 20 to about 25°C) at any desired rate.
  • the TiAl intermetallic casting preferably exhibits a duplex microstructure of the type seen in FIG. 7 . From the above, it should be evident that the casting is not required to be removed from the HIP chamber during the steps identified in FIG. 4 , and that the casting can be continuously exposed to the inert atmosphere of the HIP chamber throughout the process represented in FIG. 4 .
  • the process set forth in FIG. 5 differs from that set forth in FIG. 4 by the allowance of a full cool down (to room temperature) between the HIP cycle and the heat treatment.
  • the process of FIG. 5 additionally involves heating the casting to the T HIP1 temperature prior to the heat treatment. This process is believed to allow more flexibility in the temperature used for the HIP cycle, in that HIPing is not required to be performed at the T HIP1 temperature of FIG. 4 , but instead can be at a temperature (designated as T HIP2 ) that can be higher or lower than the temperatures within the ranges stated above for T HIP1 .
  • the process set forth in FIG. 5 generally entails HIPing a TiAl intermetallic composition (typically a casting) at a suitable temperature (T HIP2 ), which can be followed by cooling the casting to essentially any temperature (including room temperature). Thereafter, the casting is heat treated at the T HIP1 temperature (for example, at least 2300°F (about 1260°C)) for a duration sufficient to ensure the entire casting is at T HIP1 .
  • T HIP2 suitable temperature
  • T HIP1 temperature for example, at least 2300°F (about 1260°C)
  • the casting can then be cooled at a suitable rate (for example, about 5 to about 20°F/minute (about 3 to about 11°C/minute)) to a temperature of not less than 2050°F (about 1120°C), more preferably not less than 2100°F (about 1150°C), and most preferably about 2100 to about 2150°F (about 1150 to about 1175°C).
  • the casting can then be subjected to the same heat treatment as described for the process of FIG. 4 , after which the casting can be cooled directly to room temperature (about 20 to about 25°C).
  • the TiAl intermetallic casting preferably exhibits a duplex microstructure of the type seen in FIG. 7 .
  • a suitable rate for example, about 5 to about 20°F/minute (about 3 to about 11°C/minute)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Description

    BACKGROUND OF THE INVENTION
  • The present invention generally relates to compositions containing titanium and aluminum and the processing thereof. More particularly, this invention relates to methods of processing cast titanium aluminide intermetallic compositions that entail hot isostatic pressing and heat treatment to close porosity and yield a desirable microstructure.
  • Because weight and high temperature strength are primary considerations in gas turbine engine design, there is a continuing effort to create relatively light weight alloys/compositions that have high strength at elevated temperatures. Titanium-based alloy systems are well known in the art as having mechanical properties that are suitable for relatively high temperature applications. High temperature capabilities of titanium-based alloys has increased through the use of titanium intermetallic systems based on the titanium aluminide compounds Ti3Al (alpha-2 (α-2) alloys) and TiAl (gamma (y) alloys). These titanium aluminide intermetallic compounds (or, for convenience, TiAl intermetallics) are generally characterized as being relatively light weight, yet are known to be capable of exhibiting high strength, creep strength and fatigue resistance at elevated temperatures. Additions of chromium and niobium are known to promote certain properties of TiAl intermetallics, such as oxidation resistance, ductility, strength, etc. As a nonlimiting example, U.S. Patent No. 4,879,092 to Huang discloses a titanium aluminide intermetallic composition having an approximate formula of Ti46-50Al46-50Cr2Nb2, or nominally about Ti-48Al-2Cr-2Nb. This alloy, referred to herein as the 48-2-2 alloy, is considered to have a nominal temperature capability of up to about 1400°F (about 760°C), with useful but diminishing capabilities up to about 1500°F (about 815°C). In gas turbine engines used in commercial aircraft, the 48-2-2 alloy is well suited for low pressure turbine blade (LPTB) applications.
  • The production of components from TiAl intermetallics is complicated by their relatively low ductility and the typical desire for these compositions to be extrudable, forgeable, reliable and/or castable. Hot isostatic pressing (HIP) is commonly performed to eliminate internal voids and microporosity in titanium aluminide intermetallic castings. Because uncontrolled cooling rates typically performed following HIP are not effective to generate a desired microstructure, responsiveness to post-HIP heat treatments is another desirable characteristic in order to achieve microstructures and mechanical properties needed for specific applications.
  • US 6,231,699 B1 relates to a process for heat treatment of gamma titanim aluminide alloy articles.
  • HIP cycles are typically separate from the heat treatment cycle in the processing of castings. As an example, desired microstructures and mechanical properties have been obtained in castings of the 48-2-2 alloy using a process represented in FIG. 3. Following the production of the casting, a pre-HIP heat treatment is performed at a temperature within a range of about 1800 to about 2000°F (about 980 to about 1090°C) and for a duration of about five to twelve hours. Thereafter, the casting is cooled and transferred to a HIP chamber and then subjected to a high pressure HIP step (for example, 25 ksi (about 1720 bar) or more) at about 2165°F for a duration of about three hours. The HIPed casting is then cooled, removed from the HIP chamber, and then subjected to a post-HIP solution treatment at a temperature of about 2200°F for a duration of about two hours. This sequence requires the use of at least two different vessels and loading and unloading the casting three times from these vessels. In addition to incurring additional cost and cycle time, this process has been associated with the loss of aluminum from the casting surface, which leads to reduced environmental and/or mechanical properties.
  • Unexpectedly, net-shape castings that have been produced, for example, by spin casting from the 48-2-2 alloy to produce low pressure turbine blades have not responded well to the heat treatment process described above, or to other processes employed with conventional TiAl castings, such as gravity casting and overstock casting. In particular, the 48-2-2 alloy net-shape castings processed by net-shape casting methods do not develop a desirable duplex microstructure containing equiaxed and lamellar gamma TiAl morphologies that improve the ductility of the casting, particularly when the volume fraction of the lamellar structure is about 10 to about 90 percent, particularly if the volume fraction of the lamellar structure is about 20 to about 80 percent and ideally about 30 to about 70 percent. FIGS. 1 and 2 are photomicrographs showing desirable duplex microstructures present in two conventional TiAl castings.
  • In view of the above, a method is needed that is capable of processing TiAl intermetallics, including but not limited to net-shape geometries of the 48-2-2 alloy, to yield a duplex microstructure containing equiaxed and lamellar morphologies. It would be further desirable if such a method did not require a sequence in which a casting is not required to be transferred between multiple different vessels.
  • BRIEF DESCRIPTION OF THE INVENTION
  • The present invention provides methods capable of processing compositions containing titanium and aluminum, and especially titanium aluminide intermetallic compositions (TiAl intermetallics) based on the TiAl (gamma) intermetallic compound, to yield desirable microstructures. The methods have the further capability of being performed in a single vessel, resulting in a less complicated process than conventional methods used to produce compositions that require void closure (for example, by HIPing) and heat treatment.
  • According to a first aspect of the invention, a method of processing a titanium aluminide intermetallic composition includes hot isostatic pressing the titanium aluminide intermetallic composition, cooling the composition, heat treating the composition at a temperature of at least 1260°C (about 2300°F) for 2.5 to 5 hours, cooling the composition to a temperature of not less than 1150°C (2100°F), holding the composition at a hold temperature of 1150 to 1200°C (2100 to 2200°F) for a duration of two to six hours, and then cooling the composition to room temperature. Following this procedure, the titanium aluminide intermetallic composition exhibits a desirable duplex microstructure containing equiaxed and lamellar morphologies of the gamma TiAl phase.
  • A beneficial effect of the invention is the ability to produce desirable duplex microstructures in TiAl intermetallics that may otherwise be difficult to obtain, particularly if produced by net-shape casting methods such as spin casting and possibly certain other casting techniques. Another beneficial effect is the ability to take advantage of the energy available for phase equilibration during cool down from a HIP step to assist in a subsequent heat treatment, which has been determined to eliminate the requirement for conventional pre- and post-heat treatment cycles that may cause aluminum to be lost from the casting surface as well as incur additional cost and cycle time. These advantages have been particularly observed with net-shape castings produced by net- shape casting methods, such as spin casting, in the aforementioned 48-2-2 alloy, though other TiAl intermetallic compositions also benefit from the processing methods provided by the present invention.
  • Other aspects and advantages of this invention will be better appreciated from the following detailed description.
  • BRIEF DESCRIPTION OF THE DRAWINGS
    • FIG. 1 and 2 are photomicrographs showing the microstructures of two castings formed of a TiAl intermetallic composition with a desirable duplex microstructure.
    • FIG. 3 is a flow chart representing a method of processing castings formed of TiAl intermetallic compositions in accordance with a prior art HIP and heat treatment process.
    • FIGS. 4 and 5 are flow charts representing two methods of processing castings formed of TiAl intermetallic compositions in accordance with embodiments of the present invention.
    • FIGS. 6 and 7 are microphotographs showing the microstructures of two castings formed of the same TiAl intermetallic composition, wherein the casting of FIG. 6 was processed in accordance with the prior art HIP and heat treatment process of FIG. 3 and the casting of FIG. 7 was processed in accordance with the HIP and heat treatment process of FIG. 4.
    DETAILED DESCRIPTION OF THE INVENTION
  • FIGS. 4 and 5 contain flow charts that represent two related methods by which TiAl intermetallic compositions, including but not limited to the 48-2-2 alloy, can be processed to yield a desirable duplex microstructure, with the additional benefit of avoiding the disadvantages of the prior art process summarized in FIG. 3. In particular, the methods of FIGS. 4 and 5 avoid the pre- and post-HIP vacuum heat treatments that are believed to promote the loss of aluminum in TiAl intermetallic compositions. The invention also takes advantage of the high gas pressures and protective (inert) atmospheres used during HIP, the combination of which is believed to be capable of reducing the loss of aluminum in a TiAl intermetallic composition. Furthermore, each of the methods summarized in FIGS. 4 and 5 provide for interrupted cooling from a HIP step (FIG. 4) or a temperature that is believed to take advantage of the non-equilibrium phase distribution in TiAl intermetallic compositions following HIP (FIG. 5) to generate (during a subsequent heat treatment) microstructures that are capable of providing desirable mechanical properties, especially if the TiAl intermetallic composition is a cast using a net-shape casting process, such as spin casting or other means.
  • As noted above, the processes summarized in FIGS. 4 and 5 are believed to be particularly beneficial to the 48-2-2 alloy, whose composition is based on the gamma (TiAl) intermetallic compound. Castings of the 48-2-2 alloy exhibit improved ductility and other desirable properties if they contain a duplex microstructure containing equiaxed and lamellar gamma phase morphologies. FIGS. 6 and 7 are representative of LPTB castings produced from the 48-2-2 alloy. Both castings were produced by spin casting, the casting in FIG. 6 was processed by a HIP and heat treatment procedure corresponding to that represented in FIG. 3, and the casting in FIG. 7 was processed by a modified HIP and heat treatment procedure corresponding to that represented in FIG. 4. The microstructure of the heat treated casting shown in FIG. 6 possesses an excessive amount of equiaxed gamma phase and an inadequate amount of the lamellar phase (less than 10% volume fraction of the lamellar phase). Such a microstructure would yield a component with insufficiently high temperature creep strength. The microstructure of the heat treated casting shown in FIG. 7 has acceptable amounts of the equiaxed gamma phase and the lamellar phase (about 20% volume fraction of the lamellar phase), the sole exception being at the outermost surface of the casting where titanium levels are depleted. However, the outermost surface can be removed by conventional techniques, such as abrasive blasting or chemical milling, with the result that the entire remaining casting would contain acceptable amounts of the equiaxed gamma phase and lamellar phase.
  • While the invention has been shown to yield particularly advantageous results with the 48-2-2 alloy, the invention is believed to be more generally applicable to titanium aluminide intermetallic compositions, particularly TiAl (gamma) intermetallic compositions modified with elements that are intended to promote various properties. For example, the invention has also been shown to be effective with TiAl intermetallic compositions that contain tantalum. Particular compositions that have been successfully evaluated include TiAl compositions that contain chromium, niobium and/or tantalum, for example, about 1.8 to about 2 atomic percent chromium, up to about 2 atomic percent niobium, and up to about 4 atomic percent tantalum. Specific compositions that were successfully evaluated contained, in atomic percent: about 47.3% aluminum, about 1.9% chromium, about 1.9% niobium and the balance titanium and incidental impurities (roughly corresponding to the 48-2-2 alloy); or about 47.3% aluminum, about 1.8% chromium, about 0.85% niobium, about 1.7% tantalum and the balance titanium and incidental impurities; or about 47.3% aluminum, about 2.0% chromium, about 4.0% tantalum and the balance titanium and incidental impurities. More generally, the levels of titanium and aluminum in these TiAl intermetallic compositions are selected to yield a casting whose predominant constituent is the TiAl (gamma) intermetallic compound. While the compositions evaluated all contained about 47.3 atomic percent aluminum and about 46.7 to 48.9 atomic percent titanium, those skilled in the art will appreciate that aluminum and titanium levels beyond these amounts can be used to yield a casting that is entirely or predominantly the TiAl intermetallic compound, and such variations are within the scope of the invention. Furthermore, those skilled in the art will recognize that other alloy constituents could be included to modify the properties of the TiAl intermetallic compound, and such variations are also within the scope of the invention.
  • During investigations leading to the present invention, solidification modeling was conducted that suggested that areas of low pressure turbine blade (LPTB) castings formed by net-shape casting, including spin casting, solidified in less than a few seconds. It was concluded that, compared to other casting methods and/or other types of castings, such a rapid solidification rate may modify the route through the TiAl phase diagram that the alloy/composition takes during solidification and may lead to unexpected responses to conventional heat treatments that are subsequently performed on the castings. These unexpected results negatively impact the uniformity of the microstructure of net-shape cast and heat treated components, such as the chemistry and uniformity of the microstructure over the full chord and span in net-shape TiAl airfoils. The process represented in FIG. 4 combines a HIP cycle with a heat treatment without cooling to room temperature therebetween, which reestablishes phase equilbria that are capable of developing a duplex microstructure that provides desirable mechanical properties.
  • The process of FIG. 4 generally entails preparing a TiAl intermetallic composition. A preferred but not limiting example entails spin casting an appropriate melt containing the desired constituents of the TiAl intermetallic composition. The composition (casting) is then loaded in a suitable HIP chamber and heated in a protective atmosphere (for example, argon or another inert gas) to a temperature at which the casting is to undergo HIPing. According to a preferred aspect of the invention, the HIP temperature (THIPI) is at least 2300°F (about 1260°C), more preferably at least 2350°F (about 1290°C), and most preferably in a range of 2375 to 2425°F (about 1300 to about 1330°C). The pressure applied to the casting during the HIP cycle is intended to eliminate internal voids and microporosity in the castings. For this purpose, pressures of at least 15 ksi (about 1030 bar) are believed to be sufficient, with pressures of about 18 ksi (about 1240 bar) and higher believed to be particularly preferred. The duration of the HIP cycle may vary depending on the particular composition and pressure used, but suitable results are believed to be obtained with HIP cycles having durations of 2.5 to 5 hours, and particularly 2.5 to 3.5 hours.
  • Following the HIP cycle, the casting is cooled to a temperature of not less than 2100°F (1150°C), and most preferably 2100 to 2150°F (1150 to 1175°C). The cooling rate may vary, but rates of about 5 to about 20°F/minute (about 3 to about 11 °C/minute) have been found to be acceptable. Without needing to be removed from the HIP chamber, the casting then undergoes a heat treatment at a temperature of about 2100 to about 2200°F (about 1150 to about 1200°C), for example, about 2100 to about 2150°F (about 1150 to about 1175°C). The duration of this heat treatment may vary depending on the particular composition and HIP treatment used, but suitable results are believe to be obtained with heat treatment cycles having durations of about two to about six hours, and especially about 4.5 to about 5.5 hours.
  • Following heat treatment, the casting can be cooled directly to room temperature (about 20 to about 25°C) at any desired rate. At the result of this process, the TiAl intermetallic casting preferably exhibits a duplex microstructure of the type seen in FIG. 7. From the above, it should be evident that the casting is not required to be removed from the HIP chamber during the steps identified in FIG. 4, and that the casting can be continuously exposed to the inert atmosphere of the HIP chamber throughout the process represented in FIG. 4.
  • The process set forth in FIG. 5 differs from that set forth in FIG. 4 by the allowance of a full cool down (to room temperature) between the HIP cycle and the heat treatment. The process of FIG. 5 additionally involves heating the casting to the THIP1 temperature prior to the heat treatment. This process is believed to allow more flexibility in the temperature used for the HIP cycle, in that HIPing is not required to be performed at the THIP1 temperature of FIG. 4, but instead can be at a temperature (designated as THIP2) that can be higher or lower than the temperatures within the ranges stated above for THIP1.
  • In view of the above, the process set forth in FIG. 5 generally entails HIPing a TiAl intermetallic composition (typically a casting) at a suitable temperature (THIP2), which can be followed by cooling the casting to essentially any temperature (including room temperature). Thereafter, the casting is heat treated at the THIP1 temperature (for example, at least 2300°F (about 1260°C)) for a duration sufficient to ensure the entire casting is at THIP1. The casting can then be cooled at a suitable rate (for example, about 5 to about 20°F/minute (about 3 to about 11°C/minute)) to a temperature of not less than 2050°F (about 1120°C), more preferably not less than 2100°F (about 1150°C), and most preferably about 2100 to about 2150°F (about 1150 to about 1175°C). The casting can then be subjected to the same heat treatment as described for the process of FIG. 4, after which the casting can be cooled directly to room temperature (about 20 to about 25°C). As the result of this process, the TiAl intermetallic casting preferably exhibits a duplex microstructure of the type seen in FIG. 7. As with the process of FIG. 4, it should be evident that the casting is not required to be removed from the HIP chamber for any step of FIG. 5, and that the casting can be continuously exposed to the inert atmosphere of the HIP chamber throughout the process represented in FIG. 5.
    While the invention has been described in terms of particular embodiments, it is apparent that other forms could be adopted by one skilled in the art. Therefore, the scope of the invention is to be limited only by the following claims.

Claims (2)

  1. A method of processing a titanium aluminide intermetallic composition based on a TiAl intermetallic compound to yield a duplex microstructure containing equiaxed and lamellar morphologies of the gamma TiAl phase, the method comprising:
    hot isostatic pressing the titanium aluminide intermetallic composition;
    cooling the titanium aluminide intermetallic composition;
    heat treating the titanium aluminide intermetallic composition at a temperature of at least 1260°C for 2.5 to 5 hours;
    cooling the titanium aluminide intermetallic composition to a temperature of not less than 1150°C;
    holding the titanium aluminide intermetallic composition at a hold temperature of 1150 to 1200°C for a duration of two to six hours; and then
    cooling the titanium aluminide intermetallic composition to room temperature;
    wherein the titanium aluminide intermetallic composition exhibits the duplex microstructure following the step of cooling the titanium aluminide intermetallic composition to room temperature; and
    wherein the titanium aluminide intermetallic composition consists of titanium and aluminum in amounts to yield the TiAl intermetallic compound, one or more of chromium, niobium and tantalum, and incidental impurities.
  2. The method according to claim 1, wherein the titanium aluminide intermetallic composition consists of nominally Ti-48Al-2Cr-2Nb.
EP15184357.0A 2012-03-23 2013-03-19 Method for processing titanium aluminide intermetallic compositions Active EP2995695B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201261614751P 2012-03-23 2012-03-23
US13/459,420 US20130248061A1 (en) 2012-03-23 2012-04-30 Methods for processing titanium aluminide intermetallic compositions
EP13159885.6A EP2641984B1 (en) 2012-03-23 2013-03-19 Methods for processing titanium aluminide intermetallic compositions

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP13159885.6A Division-Into EP2641984B1 (en) 2012-03-23 2013-03-19 Methods for processing titanium aluminide intermetallic compositions
EP13159885.6A Division EP2641984B1 (en) 2012-03-23 2013-03-19 Methods for processing titanium aluminide intermetallic compositions

Publications (2)

Publication Number Publication Date
EP2995695A1 EP2995695A1 (en) 2016-03-16
EP2995695B1 true EP2995695B1 (en) 2017-11-22

Family

ID=47913098

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13159885.6A Active EP2641984B1 (en) 2012-03-23 2013-03-19 Methods for processing titanium aluminide intermetallic compositions
EP15184357.0A Active EP2995695B1 (en) 2012-03-23 2013-03-19 Method for processing titanium aluminide intermetallic compositions

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13159885.6A Active EP2641984B1 (en) 2012-03-23 2013-03-19 Methods for processing titanium aluminide intermetallic compositions

Country Status (6)

Country Link
US (1) US20130248061A1 (en)
EP (2) EP2641984B1 (en)
JP (1) JP6200666B2 (en)
CN (1) CN103320647B (en)
BR (1) BR102013006917A2 (en)
CA (1) CA2809444C (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US8932518B2 (en) 2012-02-29 2015-01-13 General Electric Company Mold and facecoat compositions
US10597756B2 (en) 2012-03-24 2020-03-24 General Electric Company Titanium aluminide intermetallic 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
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
CN103710606B (en) * 2013-12-16 2016-07-06 北京工业大学 A kind of containing Cr height Nb β-γ TiAl intermetallic compound material and preparation method thereof
US10391547B2 (en) 2014-06-04 2019-08-27 General Electric Company Casting mold of grading with silicon carbide
CN104005023B (en) * 2014-06-06 2016-05-25 江苏大学 Prepare the method for Ti-Al-Nb alloy coat in surface of metal titanium
ES2728527T3 (en) * 2014-09-01 2019-10-25 MTU Aero Engines AG TiAl component manufacturing procedure
FR3027921A1 (en) * 2014-10-31 2016-05-06 Snecma TITANIUM-BASED ALLOYS HAVING IMPROVED MECHANICAL PROPERTIES
FR3106851B1 (en) * 2020-01-31 2022-03-25 Safran Aircraft Engines Hot isostatic compression heat treatment of titanium aluminide alloy bars for turbomachinery low pressure turbine blades
CN111975003B (en) * 2020-08-14 2022-12-27 西北工业大学 Method for regulating and controlling titanium-aluminum alloy full lamellar structure

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879092A (en) 1988-06-03 1989-11-07 General Electric Company Titanium aluminum alloys modified by chromium and niobium and method of preparation
US5149497A (en) * 1991-06-12 1992-09-22 General Electric Company Oxidation resistant coatings of gamma titanium aluminum alloys modified by chromium and tantalum
JPH06228685A (en) * 1993-02-01 1994-08-16 Honda Motor Co Ltd High strength and high ductility tial intermetallic compound and its production
US5350466A (en) * 1993-07-19 1994-09-27 Howmet Corporation Creep resistant titanium aluminide alloy
US5634992A (en) * 1994-06-20 1997-06-03 General Electric Company Method for heat treating gamma titanium aluminide alloys
US6231699B1 (en) * 1994-06-20 2001-05-15 General Electric Company Heat treatment of gamma titanium aluminide alloys
US5609698A (en) * 1995-01-23 1997-03-11 General Electric Company Processing of gamma titanium-aluminide alloy using a heat treatment prior to deformation processing
US5545265A (en) * 1995-03-16 1996-08-13 General Electric Company Titanium aluminide alloy with improved temperature capability
CN1055323C (en) * 1997-11-03 2000-08-09 冶金工业部钢铁研究总院 Method for texture homogenization fining of Ti-Al alloy cast
JP3784363B2 (en) * 2002-10-10 2006-06-07 株式会社神戸製鋼所 Modification method of Al alloy castings
DE102007060587B4 (en) * 2007-12-13 2013-01-31 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH titanium aluminide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2641984B1 (en) 2015-10-21
EP2995695A1 (en) 2016-03-16
JP6200666B2 (en) 2017-09-20
EP2641984A3 (en) 2014-03-12
CA2809444C (en) 2021-05-18
US20130248061A1 (en) 2013-09-26
BR102013006917A2 (en) 2015-07-07
JP2013199705A (en) 2013-10-03
CN103320647B (en) 2017-11-07
CN103320647A (en) 2013-09-25
CA2809444A1 (en) 2013-09-23
EP2641984A2 (en) 2013-09-25

Similar Documents

Publication Publication Date Title
EP2995695B1 (en) Method for processing titanium aluminide intermetallic compositions
EP2112243B1 (en) High strength L12 aluminium alloys
EP2657358B1 (en) Titanium aluminide intermetallic compositions
Xu et al. Progress in application of rare metals in superalloys
US9034247B2 (en) Alumina-forming cobalt-nickel base alloy and method of making an article therefrom
US4482398A (en) Method for refining microstructures of cast titanium articles
EP2112239A2 (en) High strength aluminium alloys with L12 precipitates
EP2110453A1 (en) L12 Aluminium alloys
JPS6343459B2 (en)
CN101952467A (en) High-strength aluminum casting alloys resistant to hot tearing
US5908516A (en) Titanium Aluminide alloys containing Boron, Chromium, Silicon and Tungsten
CN109161770A (en) A kind of high-modulus magnesium alloy and preparation method thereof
Erickson Polycrystalline cast superalloys
EP2520678B1 (en) Nickel-base alloy
JP6833029B2 (en) Titanium-free superalloys, powders, methods and parts
US20100135847A1 (en) Nickel-containing alloys, method of manufacture thereof and articles derived therefrom
US20050069450A1 (en) Nickel-containing alloys, method of manufacture thereof and articles derived thereform
JP6721289B2 (en) Articles and method of manufacturing articles
US7704339B2 (en) Method of heat treating titanium aluminide
JP2000312964A (en) Casting method of single crystal superalloy product casting
SE461987B (en) PROCEDURES FOR HEAT TREATMENT OF GOODS OF HOEGHAALLFASTE ALOYES FOR HEAT ISOSTATIC PRESSURE
RU2361012C1 (en) Treatment method of cast made of heat-resistant nickel alloys for single-crystal foundaring
EP1438441B1 (en) Heat treatment of alloys having elements for improving grain boundary strength
EP1760164A1 (en) Nickel-base superalloy
RU2361011C1 (en) Processing method of casts made of heat-resistant nickel alloys for single-crystal foundaring

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AC Divisional application: reference to earlier application

Ref document number: 2641984

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17P Request for examination filed

Effective date: 20160916

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20170612

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AC Divisional application: reference to earlier application

Ref document number: 2641984

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 948463

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013029993

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20171122

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 948463

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180222

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180223

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602013029993

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: UNITED TECHNOLOGIES CORPORATION

Effective date: 20180813

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171122

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171122

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180322

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: RAYTHEON TECHNOLOGIES CORPORATION

Effective date: 20180813

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602013029993

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20220504

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230414

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250218

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250218

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250221

Year of fee payment: 13