EP3366794B1 - Ni-based superalloy - Google Patents

Ni-based superalloy Download PDF

Info

Publication number
EP3366794B1
EP3366794B1 EP18157015.1A EP18157015A EP3366794B1 EP 3366794 B1 EP3366794 B1 EP 3366794B1 EP 18157015 A EP18157015 A EP 18157015A EP 3366794 B1 EP3366794 B1 EP 3366794B1
Authority
EP
European Patent Office
Prior art keywords
phase
amount
present
temperature
specific gravity
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
EP18157015.1A
Other languages
German (de)
French (fr)
Other versions
EP3366794A1 (en
Inventor
Kyohei YOKOTA
Yoshinori Sumi
Yoshihiko Koyanagi
Hiroyuki Takabayashi
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.)
Daido Steel Co Ltd
Original Assignee
Daido Steel Co Ltd
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
Application filed by Daido Steel Co Ltd filed Critical Daido Steel Co Ltd
Publication of EP3366794A1 publication Critical patent/EP3366794A1/en
Application granted granted Critical
Publication of EP3366794B1 publication Critical patent/EP3366794B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%

Definitions

  • the present invention relates to an Ni-based superalloy suitable for application as a material of high temperature parts such as a turbine wheel.
  • a turbine wheel rotating with receiving an exhaust gas from an engine rotates at a high speed (e. g., the rotation number per minute being hundreds of thousands) under a high temperature (e. g., under a high temperature of about 950°C) and thus, it is required to be excellent in high-temperature strength properties. Therefore, as a material of the turbine wheel, an Ni-based superalloy excellent in high-temperature strength properties, particularly an Ni-based cast alloy including Inconel 713C and MAR-M246 as a representative has been mainly used.
  • the y' phase (a phase of Ni3(Al, Ti, Nb) that is an intermetallic compound) precipitating as a strengthening phase is stable up to a high temperature, it is difficult to produce the turbine wheel by forging and thus, usually, the turbine wheel is mainly produced by casting using an Ni-based cast alloy and is used in a state as cast.
  • the alloy to be used as a material for high temperature parts such as the turbine wheel, it is required to be low in specific gravity and excellent in castability, in addition to the high-temperature strength properties.
  • any Ni-based alloy sufficiently satisfying these requirements yet.
  • Patent Document 1 describes an invention concerning a "nickel-based alloy", and there is disclosed a nickel-based alloy having a composition consisting of, in terms of % by weight, Co: from 14 to 19%, Cr: from 10 to 15%, C: from 0.05 to 0.2%, Mo: from 0 to 3%, and Ti: from 3.1 to 4.5%, with the balance being Ni and unavoidable impurities, and satisfying a Ti/Al ratio of 0.85 or less.
  • this Patent Document 1 there is no disclosure regarding specific means for improving the castability and the component compositions in individual Examples are all different from those of the present invention.
  • Patent Document 1 JP-A-2015-101753
  • the present invention has been made for the purpose of providing an Ni-based superalloy that is low in specific gravity and excellent in high-temperature strength properties and castability.
  • First aspect of the present invention is an Ni-based superalloy having a composition containing, in terms of % by mass, C: from 0.1 to 0.3%, Cr: from 8.0 to 12.0%, Mo: from 1.0 to 5.0%, Co: from 10.0 to 20.0%, Ta: from 0.01 to 1.50%, Ti: from 2.0 to 4.2%, Al: from 5.0 to 8.0%, V: from 0 to 1.5%, B: from 0.005 to 0.030%, and Zr: from 0.05 to 0.15%, with the balance being Ni and unavoidable impurities, and satisfying, in terms of atom%, Ti+Al being from 16.0 to 20.3% and Ti/Al being 0.3 or less.
  • Second aspect of the present invention is the Ni-based superalloy according to the first aspect, having a specific gravity of 7.9 g/cm 3 or less.
  • Third aspect of the present invention is the Ni-based superalloy according to the first or second aspect, in which Ta is from 0.3 to 0.8% by mass.
  • the precipitation temperature of the ⁇ ' phase can be lowered by decreasing a Ti/Al ratio that is a ratio of Ti to Al and in addition, in the case where the Ti/Al ratio is controlled to 0.3 or less, cast cracking can be prevented with suppressing the precipitation of the ⁇ ' phase in a temperature region where cracking due to insufficient ductility may occur during casting.
  • the present invention has been made based on such findings and is characterized in that the addition amount of the solid solution strengthening elements are decreased and, on the other hand, the total amount of Ti+Al that are constituent elements of the ⁇ '-phase is controlled to 16.0% or more and the Ti/Al ratio is controlled to 0.3 or less.
  • a decrease in the specific gravity of the alloy is attained by decreasing the addition amount of the solid solution strengthening elements and, on the other hand, the high-temperature strength properties are secured by increasing the addition amount of Ti and Al that are constituent elements of the ⁇ '-phase.
  • the addition amount of Ti and Al is increased, the cast cracking is prone to occur and there is a concern of inviting deterioration of the castability.
  • the Ni-based superalloy of the present invention is low in the specific gravity and excellent in the high-temperature strength properties and the castability, and hence can be suitably used as a material for high temperature parts such as a turbine wheel.
  • C improves grain boundary strength through formation of carbides. For attaining sufficient high-temperature strength, it is necessary to add C in an amount of 0.1% or more. However, excessive addition of C forms coarse eutectic carbides to cause a decrease in toughness and ductility. Therefore, an upper limit is set to 0.3%.
  • Cr forms a dense oxide film composed of Cr 2 O 3 on a surface to improve oxidation resistance and high-temperature corrosion resistance. For exhibiting such properties, it is necessary to contain Cr in an amount of 8.0% or more.
  • an upper limit is set to 12.0%. More preferable content of Cr is from 9.0 to 10.0%.
  • Mo has an effect of forming a solid solution in the austenite phase to strengthen the matrix through solid solution strengthening.
  • it is necessary to contain Mo in an amount of at least 1.0%. More preferably, the amount of Mo is 3.1% or more. However, its excessive addition lowers phase stability and deteriorates the ductility and the toughness. Therefore, an upper limit is 5.0%.
  • Co has effects of strengthening the austenite phase through solid solution strengthening and also forming a solid solution in the ⁇ ' phase to strengthen the ⁇ ' phase.
  • the amount of Co is 12.0% or more.
  • an upper limit is 20.0%.
  • Ta from 0.01 to 1.50%
  • Ta not only combines with C to form a carbide but also has an effect of forming a solid solution in the ⁇ ' phase to strengthen the ⁇ ' phase.
  • an upper limit is set to 1.50%. More preferable content is from 0.3 to 0.8%.
  • Ti combines with Ni to form the ⁇ ' phase (Ni 3 (Al, Ti) intermetallic compound) that is effective for improving strength, thereby strengthening the alloy through precipitation strengthening.
  • ⁇ ' phase Ni 3 (Al, Ti) intermetallic compound
  • an addition of Ti in a large amount increases an eutectic carbide to lower the ductility. Therefore, an upper limit is set to 4.2%. More preferable content is 3.0% or less.
  • Al is a component that forms the ⁇ ' phase (Ni 3 Al intermetallic compound).
  • Ni 3 Al intermetallic compound Ni 3 Al intermetallic compound.
  • an upper limit is set to 8.0%. More preferable content is from 6.8 to 7.5%.
  • V forms a solid solution in the ⁇ ' phase to achieve solid solution strengthening.
  • its excessive addition lowers the high-temperature strength. Therefore, 1.5% is an upper limit.
  • V is not contained.
  • B strengthens a grain boundary, it is added in an amount of 0.005% or more. However, an excessive addition of B forms a boride to lower properties. Therefore, an upper limit is set to 0.030%.
  • Zr improves the creep strength through grain boundary strengthening similarly to B, Zr is added in an amount of 0.05% or more. However, an excessive addition of Zr lowers the ductility. Therefore, an upper limit is set to 0.15%.
  • Ti+Al from 16.0 to 20.3%
  • the total amount of Ti+Al is an index that indicates the amount of the ⁇ ' phase and, for improving the high-temperature strength properties, it is necessary to contain Ti+Al in an amount of 16% or more in terms of atom %. However, their excessive addition lowers the ductility. Therefore, an upper limit is set to 20.3%.
  • the Ti/Al ratio is an important factor for the precipitation temperature of the ⁇ ' phase and, in the present invention, the Ti/Al ratio is set to 0.3 or less.
  • an Ni-based superalloy that is low in specific gravity and excellent in high-temperature strength properties and castability can be provided.
  • each of alloys having chemical compositions shown in Table 1 was melted in a vacuum melting furnace to cast 50 kg of an ingot. Thereafter, a specimen was prepared from the ingot by machining and, by using the specimen, specific gravity, 0.2% proof strength, elongation, and creep strength were evaluated. Moreover, by using each of the alloys having chemical compositions shown in Table 1, a turbine wheel was prepared to evaluate castability.
  • Measurement of specific gravity was carried out in accordance with JIS Z 8807 (2012) and evaluation was performed according to the following criteria.
  • a specimen having a parallel part diameter of 8 mm and a gauge length of 40 mm was prepared in accordance with JIS G 0567 (2012) and a tensile test was performed at a test temperature of 1,050°C. In this test, 0.2% proof strength and elongation at 1,050°C were measured.
  • the 0.2% proof strength was evaluated according to the following criteria.
  • the elongation was evaluated according to the following criteria.
  • a specimen in accordance with JIS Z 2271 (2010) was prepared, a load stress of 180 MPa was imparted thereto at a test temperature of 1,000°C to measure a life until rupture, and evaluation was performed according to the following criteria.
  • the specimen has a diameter of 6.4 mm at a parallel part.
  • Comparative Example 1 Co and Ta that are solid solution strengthening elements were not added, as compared to the composition of the present invention. Moreover, the amount of Ti that is a constituent element of the ⁇ ' phase was lower than the lower limit of the present invention, while Nb that is not added in the present invention was added. In Comparative Example 1, sufficient high-temperature strength properties were not obtained and the 0.2% proof strength and the creep strength were evaluated as "C”. Furthermore, the specific gravity was evaluated as "B", which is inferior to Examples to be mentioned later.
  • Comparative Example 2 the amount of Ti and the total amount of Ti+Al were lower than the lower limits of the present invention, while a heavy element W that is not added in the present invention was added. Therefore, in Comparative Example 2, the 0.2% proof strength and the creep strength were good as evaluated as "A” but the specific gravity was evaluated as "C".
  • Comparative Example 3 the amount of Ti and the total amount of Ti+Al were lower than the lower limits of the present invention, while heavy elements Hf and W that are not added in the present invention were added. Moreover, the amount of Ta was also higher than the upper limit 1.5% of the present invention. Therefore, in Comparative Example 3, the 0.2% proof strength, elongation and creep strength were good as evaluated as "A” but the specific gravity was evaluated as "C".
  • Comparative Example 4 the total amount of Ti+Al fell within the defined range of the present invention, while the Ti/Al ratio was higher than the upper limit 0.3 of the present invention. Therefore, in Comparative Example 4, the precipitation temperature of the ⁇ ' phase was higher than that in the other examples, so that occurrence of solidification cracking (cast cracking) was observed in the castability evaluation and the evaluation was "C". Moreover, since the precipitation temperature of the ⁇ ' phase was high, the ductility at a high temperature was low and hot elongation was also evaluated as "C".
  • Comparative Example 5 the amount of Al and the total amount of Ti+Al were lower than the lower limits of the present invention. Therefore, sufficient high-temperature strength properties were not obtained, and the 0.2% proof strength and the creep strength were evaluated as "C”. Moreover, the total amount of Ti+Al itself was small in Comparative Example 5 but the Ti/Al ratio was higher than the upper limit 0.3 of the present invention as in Comparative Example 4, so that the occurrence of cast cracking was observed and the castability was evaluated as "B".
  • Comparative Example 8 is different from aforementioned Comparative Examples 6 and 7 and Ta was added so as to fall within the component range defined in the present invention but the total amount of Ti+Al was still lower than the lower limit 16% of the present invention. Therefore, the creep strength was improved as compared to that in Comparative Examples 6 and 7 but was evaluated as "B". In Comparative Example 8, in addition to the creep strength, the 0.2% proof strength, elongation and castability were also evaluated as "B". Thus, properties as a whole were poor as compared to those of Examples to be mentioned later.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Description

    TECHNICAL FIELD
  • The present invention relates to an Ni-based superalloy suitable for application as a material of high temperature parts such as a turbine wheel.
  • BACKGROUND ART
  • For example, a turbine wheel rotating with receiving an exhaust gas from an engine rotates at a high speed (e. g., the rotation number per minute being hundreds of thousands) under a high temperature (e. g., under a high temperature of about 950°C) and thus, it is required to be excellent in high-temperature strength properties.
    Therefore, as a material of the turbine wheel, an Ni-based superalloy excellent in high-temperature strength properties, particularly an Ni-based cast alloy including Inconel 713C and MAR-M246 as a representative has been mainly used.
  • As strengthening mechanisms for high-temperature strength in the Ni-based superalloy, solid solution strengthening and y' phase (gamma prime phase) precipitation strengthening have been used. Since the y' phase (a phase of Ni3(Al, Ti, Nb) that is an intermetallic compound) precipitating as a strengthening phase is stable up to a high temperature, it is difficult to produce the turbine wheel by forging and thus, usually, the turbine wheel is mainly produced by casting using an Ni-based cast alloy and is used in a state as cast.
  • Incidentally, in a rotating body such as the turbine wheel, as the weight of the part increases, inertial weight increases and, for example, response at the rise of rotation becomes slow. Therefore, it is requested to be light in weight, that is, low in specific gravity.
    In the Ni-based alloy using the solid solution strengthening and the y' phase precipitation strengthening as strengthening mechanisms as mentioned above, the high-temperature strength is improved with an increase in the addition amount of solid solution strengthening elements. However, since specific gravity increases, it is difficult to cope with the request for a decrease in the specific gravity.
    It is also considered to decrease the specific gravity while maintaining the high-temperature strength by decreasing the addition amount of the solid solution strengthening elements and, on the other hand, increasing the addition amount of constituent elements of the γ'-phase. However, there is a problem in that, in the case where the precipitation amount of the y' phase is increased, cast cracking is prone to occur during the solidification process at casting and thus productivity becomes worse.
  • As described above, in the alloy to be used as a material for high temperature parts such as the turbine wheel, it is required to be low in specific gravity and excellent in castability, in addition to the high-temperature strength properties. However, there has not been provided any Ni-based alloy sufficiently satisfying these requirements yet.
  • Incidentally, as a prior art with regard to the present invention, the following Patent Document 1 describes an invention concerning a "nickel-based alloy", and there is disclosed a nickel-based alloy having a composition consisting of, in terms of % by weight, Co: from 14 to 19%, Cr: from 10 to 15%, C: from 0.05 to 0.2%, Mo: from 0 to 3%, and Ti: from 3.1 to 4.5%, with the balance being Ni and unavoidable impurities, and satisfying a Ti/Al ratio of 0.85 or less. However, in this Patent Document 1, there is no disclosure regarding specific means for improving the castability and the component compositions in individual Examples are all different from those of the present invention.
  • Patent Document 1: JP-A-2015-101753
  • SUMMARY OF THE INVENTION
  • With the above circumstances as a background, the present invention has been made for the purpose of providing an Ni-based superalloy that is low in specific gravity and excellent in high-temperature strength properties and castability.
  • First aspect of the present invention is an Ni-based superalloy having a composition containing, in terms of % by mass, C: from 0.1 to 0.3%, Cr: from 8.0 to 12.0%, Mo: from 1.0 to 5.0%, Co: from 10.0 to 20.0%, Ta: from 0.01 to 1.50%, Ti: from 2.0 to 4.2%, Al: from 5.0 to 8.0%, V: from 0 to 1.5%, B: from 0.005 to 0.030%, and Zr: from 0.05 to 0.15%, with the balance being Ni and unavoidable impurities, and satisfying, in terms of atom%, Ti+Al being from 16.0 to 20.3% and Ti/Al being 0.3 or less.
  • Second aspect of the present invention is the Ni-based superalloy according to the first aspect, having a specific gravity of 7.9 g/cm3 or less.
  • Third aspect of the present invention is the Ni-based superalloy according to the first or second aspect, in which Ta is from 0.3 to 0.8% by mass.
  • In an Ni-based superalloy having a γ' phase as a strengthening phase, it is known that the precipitation amount of the γ' phase is increased with an increase of the addition amount of Al and Ti that are constituent elements of the γ'-phase, and further the precipitation temperature of the γ' phase is also raised accompanied thereby.
    The present inventors made intensive investigations to pursue possibility of lowering the precipitation temperature of the γ' phase while maintaining the total amount of Al+Ti high. As a result, they found that the precipitation temperature of the γ' phase can be lowered by decreasing a Ti/Al ratio that is a ratio of Ti to Al and in addition, in the case where the Ti/Al ratio is controlled to 0.3 or less, cast cracking can be prevented with suppressing the precipitation of the γ' phase in a temperature region where cracking due to insufficient ductility may occur during casting.
  • The present invention has been made based on such findings and is characterized in that the addition amount of the solid solution strengthening elements are decreased and, on the other hand, the total amount of Ti+Al that are constituent elements of the γ'-phase is controlled to 16.0% or more and the Ti/Al ratio is controlled to 0.3 or less.
    In the present invention, a decrease in the specific gravity of the alloy is attained by decreasing the addition amount of the solid solution strengthening elements and, on the other hand, the high-temperature strength properties are secured by increasing the addition amount of Ti and Al that are constituent elements of the γ'-phase. When the addition amount of Ti and Al is increased, the cast cracking is prone to occur and there is a concern of inviting deterioration of the castability. However, in the present invention, by controlling the Ti/Al ratio to 0.3 or less, a rise in the precipitation temperature of the γ' phase is suppressed and the occurrence of the cast cracking during the solidification process is prevented, thereby securing the castability.
  • As above, the Ni-based superalloy of the present invention is low in the specific gravity and excellent in the high-temperature strength properties and the castability, and hence can be suitably used as a material for high temperature parts such as a turbine wheel.
  • MODE FOR CARRYING OUT THE INVENTION
  • The following will describe reasons for the limitation of individual components of the Ni-based superalloy in the present invention.
  • C: from 0.1 to 0.3%
  • C improves grain boundary strength through formation of carbides. For attaining sufficient high-temperature strength, it is necessary to add C in an amount of 0.1% or more. However, excessive addition of C forms coarse eutectic carbides to cause a decrease in toughness and ductility. Therefore, an upper limit is set to 0.3%.
  • Cr: from 8.0 to 12.0%
  • Cr forms a dense oxide film composed of Cr2O3 on a surface to improve oxidation resistance and high-temperature corrosion resistance. For exhibiting such properties, it is necessary to contain Cr in an amount of 8.0% or more.
  • Although the oxidation resistance and high-temperature corrosion resistance become excellent as the content of Cr increases, its excessive addition lowers phase stability and deteriorates ductility and toughness. Therefore, an upper limit is set to 12.0%. More preferable content of Cr is from 9.0 to 10.0%.
  • Mo: from 1.0 to 5.0%
  • Mo has an effect of forming a solid solution in the austenite phase to strengthen the matrix through solid solution strengthening. For the purpose, it is necessary to contain Mo in an amount of at least 1.0%. More preferably, the amount of Mo is 3.1% or more. However, its excessive addition lowers phase stability and deteriorates the ductility and the toughness. Therefore, an upper limit is 5.0%.
  • Co: form 10.0 to 20.0%
  • Co has effects of strengthening the austenite phase through solid solution strengthening and also forming a solid solution in the γ' phase to strengthen the γ' phase. For the purpose, it is necessary to contain Co in an amount of at least 10.0%.
  • More preferably, the amount of Co is 12.0% or more. However, since Co is an expensive material, it is disadvantageous in cost to add Co in a large amount. Therefore, an upper limit is 20.0%.
  • Ta: from 0.01 to 1.50%
  • Ta not only combines with C to form a carbide but also has an effect of forming a solid solution in the γ' phase to strengthen the γ' phase. For the purpose, it is necessary to contain Ta in an amount of at least 0.01%. However, since an addition of Ta in a large amount increases the specific gravity, an upper limit is set to 1.50%. More preferable content is from 0.3 to 0.8%.
  • Ti: from 2.0 to 4.2%
  • Ti combines with Ni to form the γ' phase (Ni3(Al, Ti) intermetallic compound) that is effective for improving strength, thereby strengthening the alloy through precipitation strengthening. For the purpose, it is necessary to contain Ti in an amount of at least 2.0%. However, an addition of Ti in a large amount increases an eutectic carbide to lower the ductility. Therefore, an upper limit is set to 4.2%. More preferable content is 3.0% or less.
  • Al: from 5.0 to 8.0%
  • Al is a component that forms the γ' phase (Ni3Al intermetallic compound). For obtaining sufficient high-temperature strength, it is necessary to contain Al in an amount of 5.0% or more. However, an excessive increase in the addition amount of Al lowers creep strength. Therefore, an upper limit is set to 8.0%. More preferable content is from 6.8 to 7.5%.
  • V: from 0 to 1.5%
  • V forms a solid solution in the γ' phase to achieve solid solution strengthening. However, its excessive addition lowers the high-temperature strength. Therefore, 1.5% is an upper limit. In the present invention, there is a case where V is not contained.
  • B: from 0.005 to 0.030%
  • Since B strengthens a grain boundary, it is added in an amount of 0.005% or more. However, an excessive addition of B forms a boride to lower properties. Therefore, an upper limit is set to 0.030%.
  • Zr: from 0.05 to 0.15%
  • Since Zr improves the creep strength through grain boundary strengthening similarly to B, Zr is added in an amount of 0.05% or more. However, an excessive addition of Zr lowers the ductility. Therefore, an upper limit is set to 0.15%.
  • Ti+Al: from 16.0 to 20.3% Ti/Al: 0.3 or less
  • As is explained above, the total amount of Ti+Al is an index that indicates the amount of the γ' phase and, for improving the high-temperature strength properties, it is necessary to contain Ti+Al in an amount of 16% or more in terms of atom %. However, their excessive addition lowers the ductility. Therefore, an upper limit is set to 20.3%. The Ti/Al ratio is an important factor for the precipitation temperature of the γ' phase and, in the present invention, the Ti/Al ratio is set to 0.3 or less. In the case where the total amount of Ti+Al is 16% or more and the Ti/Al ratio exceeds 0.3, the precipitation temperature of the γ' phase rises and cracking due to insufficient ductility is prone to occur during the solidification process in the casting step.
  • According to the present invention as described above, an Ni-based superalloy that is low in specific gravity and excellent in high-temperature strength properties and castability can be provided.
  • EXAMPLES The following will explain Examples of the present invention.
  • First, each of alloys having chemical compositions shown in Table 1 was melted in a vacuum melting furnace to cast 50 kg of an ingot. Thereafter, a specimen was prepared from the ingot by machining and, by using the specimen, specific gravity, 0.2% proof strength, elongation, and creep strength were evaluated. Moreover, by using each of the alloys having chemical compositions shown in Table 1, a turbine wheel was prepared to evaluate castability.
    Figure imgb0001
  • Specific Gravity Measurement
  • Measurement of specific gravity was carried out in accordance with JIS Z 8807 (2012) and evaluation was performed according to the following criteria.
    1. A: Specific gravity is 7.9 g/cm3 or less
    2. B: Specific gravity is more than 7.9 g/cm3 and 8.0 g/cm3 or less
    3. C: Specific gravity is more than 8.0 g/cm3
    High-Temperature Tensile Test
  • A specimen having a parallel part diameter of 8 mm and a gauge length of 40 mm was prepared in accordance with JIS G 0567 (2012) and a tensile test was performed at a test temperature of 1,050°C. In this test, 0.2% proof strength and elongation at 1,050°C were measured.
  • The 0.2% proof strength was evaluated according to the following criteria.
    1. A: 0.2% Proof strength is 200 MPa or more
    2. B: 0.2% Proof strength is 150 MPa or more and less than 200 MPa
    3. C: 0.2% Proof strength is less than 150 MPa
  • Also, the elongation was evaluated according to the following criteria.
    1. A: Elongation is 15% or more
    2. B: Elongation is 10% or more and less than 15%
    3. C: Elongation is less than 10%
    Creep Rupture Test
  • A specimen in accordance with JIS Z 2271 (2010) was prepared, a load stress of 180 MPa was imparted thereto at a test temperature of 1,000°C to measure a life until rupture, and evaluation was performed according to the following criteria. The specimen has a diameter of 6.4 mm at a parallel part.
    1. A: Rupture life is 25 h or more
    2. B: Rupture life is 15 h or more and less than 25 h
    3. C: Rupture life is less than 15 h
    Castability Evaluation
  • By using each of the alloys having chemical compositions shown in Table 1, turbine wheels having the same shape and the same size were cast under reduced pressure under the same conditions. For 100 pieces of the turbine wheels prepared by using the alloy having the same alloy composition, the occurrence of cracking at edges was visually confirmed and evaluation was performed according to the following criteria.
    1. A: No occurrence of cracking was observed
    2. B: Incidence of turbine wheels on which cracking is observed is less than 30%
    3. C: Incidence of turbine wheels on which cracking is observed is 30% or more
      These results are shown in Table 2.
      Figure imgb0002
  • In Comparative Example 1, Co and Ta that are solid solution strengthening elements were not added, as compared to the composition of the present invention. Moreover, the amount of Ti that is a constituent element of the γ' phase was lower than the lower limit of the present invention, while Nb that is not added in the present invention was added. In Comparative Example 1, sufficient high-temperature strength properties were not obtained and the 0.2% proof strength and the creep strength were evaluated as "C". Furthermore, the specific gravity was evaluated as "B", which is inferior to Examples to be mentioned later.
  • In Comparative Example 2, the amount of Ti and the total amount of Ti+Al were lower than the lower limits of the present invention, while a heavy element W that is not added in the present invention was added. Therefore, in Comparative Example 2, the 0.2% proof strength and the creep strength were good as evaluated as "A" but the specific gravity was evaluated as "C".
  • In Comparative Example 3, the amount of Ti and the total amount of Ti+Al were lower than the lower limits of the present invention, while heavy elements Hf and W that are not added in the present invention were added. Moreover, the amount of Ta was also higher than the upper limit 1.5% of the present invention. Therefore, in Comparative Example 3, the 0.2% proof strength, elongation and creep strength were good as evaluated as "A" but the specific gravity was evaluated as "C".
  • In Comparative Example 4, the total amount of Ti+Al fell within the defined range of the present invention, while the Ti/Al ratio was higher than the upper limit 0.3 of the present invention. Therefore, in Comparative Example 4, the precipitation temperature of the γ' phase was higher than that in the other examples, so that occurrence of solidification cracking (cast cracking) was observed in the castability evaluation and the evaluation was "C". Moreover, since the precipitation temperature of the γ' phase was high, the ductility at a high temperature was low and hot elongation was also evaluated as "C".
  • In Comparative Example 5, the amount of Al and the total amount of Ti+Al were lower than the lower limits of the present invention. Therefore, sufficient high-temperature strength properties were not obtained, and the 0.2% proof strength and the creep strength were evaluated as "C". Moreover, the total amount of Ti+Al itself was small in Comparative Example 5 but the Ti/Al ratio was higher than the upper limit 0.3 of the present invention as in Comparative Example 4, so that the occurrence of cast cracking was observed and the castability was evaluated as "B".
  • In Comparative Examples 6 and 7, the total amount of Ti+Al was large as compared to that in Comparative Example 5 but the amount was still lower than the lower limit 16% of the present invention. In addition, Ta was not added. Therefore, the creep strength was evaluated as "C".
  • Comparative Example 8 is different from aforementioned Comparative Examples 6 and 7 and Ta was added so as to fall within the component range defined in the present invention but the total amount of Ti+Al was still lower than the lower limit 16% of the present invention. Therefore, the creep strength was improved as compared to that in Comparative Examples 6 and 7 but was evaluated as "B". In Comparative Example 8, in addition to the creep strength, the 0.2% proof strength, elongation and castability were also evaluated as "B". Thus, properties as a whole were poor as compared to those of Examples to be mentioned later.
  • On the other hand, in Examples 1 to 14 in which individual elements satisfied the component ranges of the present invention, the specific gravity was evaluated as "A" in all the cases and thus was good. Moreover, the 0.2% proof strength, elongation and creep strength were evaluated as all "A" or, for only one item, "B", which are considered as good. Furthermore, in all Examples, there was no problem in castability, which was evaluated as "A". Thus, the alloys of Examples were low in specific gravity (7.9 g/cm3 or less in all the alloys), had high high-temperature strength properties in a high temperature region in the vicinity of 1,000°C, and also had castability. Particularly, in Examples 1, 2, 5, 10, and 14 in which individual elements satisfied more preferable ranges, all the evaluation items are evaluated as "A" and alloys excellent in balance were obtained.

Claims (4)

  1. An Ni-based superalloy having a composition,
    consisting of: in terms of % by mass,
    C: from 0.1 to 0.3%,
    Cr: from 8.0 to 12.0%,
    Mo: from 1.0 to 5.0%,
    Co: from 10.0 to 20.0%,
    Ta: from 0.01 to 1.50%,
    Ti: from 2.0 to 4.2%,
    Al: from 5.0 to 8.0%,
    V: from 0 to 1.5%,
    B: from 0.005 to 0.030%, and
    Zr: from 0.05 to 0.15%,
    with the balance being Ni and unavoidable impurities, and satisfying, in terms of atom%,
    Ti+Al being from 16.0 to 20.3% and
    Ti/Al being 0.3 or less.
  2. The Ni-based superalloy according to claim 1, having a specific gravity of 7.9 g/cm3 or less.
  3. The Ni-based superalloy according to claim 1 or 2, wherein the content of Ta is from 0.3 to 0.8% by mass.
  4. Use of the Ni-based superalloy according to one of claims 1 to 3, for manufacturing a turbine wheel.
EP18157015.1A 2017-02-24 2018-02-15 Ni-based superalloy Active EP3366794B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2017033971A JP6769341B2 (en) 2017-02-24 2017-02-24 Ni-based superalloy

Publications (2)

Publication Number Publication Date
EP3366794A1 EP3366794A1 (en) 2018-08-29
EP3366794B1 true EP3366794B1 (en) 2019-06-19

Family

ID=61226511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18157015.1A Active EP3366794B1 (en) 2017-02-24 2018-02-15 Ni-based superalloy

Country Status (4)

Country Link
US (1) US10385426B2 (en)
EP (1) EP3366794B1 (en)
JP (1) JP6769341B2 (en)
CN (1) CN108504903B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3867416A4 (en) * 2019-11-22 2022-11-23 Raytheon Technologies Corporation Metallic alloy

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4608094A (en) * 1984-12-18 1986-08-26 United Technologies Corporation Method of producing turbine disks
JP3753143B2 (en) * 2003-03-24 2006-03-08 大同特殊鋼株式会社 Ni-based super heat-resistant cast alloy and turbine wheel using the same
US20080260570A1 (en) * 2004-12-02 2008-10-23 Hiroshi Harada Heat-Resistant Superalloy
JP4885530B2 (en) * 2005-12-09 2012-02-29 株式会社日立製作所 High strength and high ductility Ni-base superalloy, member using the same, and manufacturing method
CN100543164C (en) * 2007-04-25 2009-09-23 中国科学院金属研究所 A kind of directional solidification heat corrosion resistant nickel base cast superalloy and preparation method thereof
CN101974708A (en) * 2010-11-05 2011-02-16 钢铁研究总院 Hot erosion resisting directionally solidified nickel-based cast superalloy
US10266926B2 (en) * 2013-04-23 2019-04-23 General Electric Company Cast nickel-base alloys including iron
JP6213185B2 (en) 2013-11-25 2017-10-18 株式会社Ihi Nickel base alloy
JP6634674B2 (en) * 2014-02-28 2020-01-22 大同特殊鋼株式会社 Turbine wheel for automotive turbocharger and method of manufacturing the same

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
JP2018138690A (en) 2018-09-06
EP3366794A1 (en) 2018-08-29
CN108504903A (en) 2018-09-07
US10385426B2 (en) 2019-08-20
US20180245188A1 (en) 2018-08-30
CN108504903B (en) 2020-07-28
JP6769341B2 (en) 2020-10-14

Similar Documents

Publication Publication Date Title
JP5177559B2 (en) Ni-based single crystal superalloy
US8226886B2 (en) Nickel-based superalloys and articles
US8734716B2 (en) Heat-resistant superalloy
US9738953B2 (en) Hot-forgeable Ni-based superalloy excellent in high temperature strength
JP5696995B2 (en) Heat resistant superalloy
JP5869034B2 (en) Nickel superalloys and parts made from nickel superalloys
EP1795621B1 (en) High-strength and high-ductility ni-base superalloys, parts using them, and method of producing the same
US20110268989A1 (en) Cobalt-nickel superalloys, and related articles
US20130206287A1 (en) Co-based alloy
EP2479302B1 (en) Ni-based heat resistant alloy, gas turbine component and gas turbine
JP5418589B2 (en) Ni-based single crystal superalloy and turbine blade using the same
EP3366794B1 (en) Ni-based superalloy
US20170051382A1 (en) Optimized nickel-based superalloy
JP2012532982A (en) Nickel-base superalloy
US20100329921A1 (en) Nickel base superalloy compositions and superalloy articles
JP6213185B2 (en) Nickel base alloy
JP2023018394A (en) Ni-BASED SUPERALLOY, AND TURBINE WHEEL
WO2017154809A1 (en) Ni-BASED UNIDIRECTIONALLY SOLIDIFIED ALLOY

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180215

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

AX Request for extension of the european patent

Extension state: BA ME

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 19/05 20060101AFI20190129BHEP

INTG Intention to grant announced

Effective date: 20190219

RIN1 Information on inventor provided before grant (corrected)

Inventor name: YOKOTA, KYOHEI

Inventor name: TAKABAYASHI, HIROYUKI

Inventor name: KOYANAGI, YOSHIHIKO

Inventor name: SUMI, YOSHINORI

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

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: DE

Ref legal event code: R096

Ref document number: 602018000150

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1145608

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190715

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190619

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

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: 20190619

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: 20190619

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: 20190619

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: 20190619

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: 20190619

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: 20190919

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

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: 20190920

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: 20190619

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: 20190619

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: 20190919

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1145608

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190619

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

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: 20190619

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: 20190619

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: 20190619

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: 20190619

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: 20190619

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: 20190619

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: 20191021

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: 20190619

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: 20191019

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: 20190619

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: 20190619

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: 20190619

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

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: 20190619

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: 20190619

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

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: 20200224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018000150

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

26N No opposition filed

Effective date: 20200603

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

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: 20190619

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200229

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: 20200215

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: 20190619

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: 20200229

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

Ref country code: LI

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

Effective date: 20210228

Ref country code: CH

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

Effective date: 20210228

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190619

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: 20190619

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190619

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

Ref country code: IE

Payment date: 20230110

Year of fee payment: 6

Ref country code: FR

Payment date: 20230110

Year of fee payment: 6

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

Ref country code: DE

Payment date: 20231228

Year of fee payment: 7

Ref country code: GB

Payment date: 20240108

Year of fee payment: 7