[go: up one dir, main page]

EP3521467B1 - Alliage de plaque d'aluminium-lithium à faible densité, à faible coût, essentiellement exempt d'ag et de zn, pour application aérospatiale - Google Patents

Alliage de plaque d'aluminium-lithium à faible densité, à faible coût, essentiellement exempt d'ag et de zn, pour application aérospatiale Download PDF

Info

Publication number
EP3521467B1
EP3521467B1 EP19155140.7A EP19155140A EP3521467B1 EP 3521467 B1 EP3521467 B1 EP 3521467B1 EP 19155140 A EP19155140 A EP 19155140A EP 3521467 B1 EP3521467 B1 EP 3521467B1
Authority
EP
European Patent Office
Prior art keywords
aluminum
alloy
stock
lithium alloy
lithium
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
EP19155140.7A
Other languages
German (de)
English (en)
Other versions
EP3521467A1 (fr
Inventor
Zhengdong Long
Philippe Lassince
Robert A. Matuska
Florence Andrea BALDWIN
David J. Shoemaker
Ravi Rastogi
Roy A. Nash
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.)
Kaiser Aluminum Fabricated Products LLC
Original Assignee
Kaiser Aluminum Fabricated Products LLC
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 Kaiser Aluminum Fabricated Products LLC filed Critical Kaiser Aluminum Fabricated Products LLC
Publication of EP3521467A1 publication Critical patent/EP3521467A1/fr
Application granted granted Critical
Publication of EP3521467B1 publication Critical patent/EP3521467B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent

Definitions

  • the present invention generally relates to Aluminum-Copper-Lithium-Magnesium based alloy products.
  • Al-lithium (Al-Li) plate products that meet all above requirements.
  • Al-Li alloys capable of producing higher than 0.5" thickness plate products.
  • the examples of existing alloys are 2050 (up to 6.5" thickness), 2195 (up to 2.25" thickness), 2060 (up to 1.5" thickness), 2395 (up to 1.5" thickness) and 2196 (up to 1.0" thickness) based on “Registration Record Series - Tempers for Aluminum and Aluminum Alloys Production” published in 2011 and “Addendum to 2011 Tan Sheets of Registration Record Series - Tempers for Aluminum and Aluminum Alloys Production” published in 2017 by The Aluminum Association. It should be mentioned that all above Al-Li plate alloys are high cost Ag containing alloys. Silver (Ag) is added to many new generation Al-Li alloys in order to improve the final product properties.
  • the Li is the most critical element for Al-Li alloys. Too low of a level of Li cannot reduce the density and improve the properties enough. However, too high of a level of Li can cause undesirable performance such as low short transverse fracture toughness, and high anisotropy of tensile properties.
  • the Cu is another important element and has to be controlled within a certain range for desirable product performance.
  • the Mg is another element to be added in a certain range in order to primarily enhance the strength and secondarily reduce the density.
  • the Zn is also another element to be considered for Al-Li alloy.
  • the addition of Zn can also negatively impact the density.
  • WO2017137260 relates to an aluminium alloy wrought product for structural members having a chemical composition consisting of, in wt.%: Cu 3.2% to 4.4%, Li 0.8% to 1.4%, Mg 0.20% to 0.90%, Mn 0.10% to 0.8%, Zn 0.20% to 0.80%, one or more elements selected from the group consisting of: (Zr 0.05% to 0.25%, Cr 0.05% to 0.30%, Ti 0.01% to 0.25%, Sc 0.05% to 0.4%, Hf 0.05% to 0.4%), Ag ⁇ 0.08%, Fe ⁇ 0.15%, Si ⁇ 0.15%, unavoidable impurities and balance aluminium.
  • the present invention provides a low cost, high performance, high Mg, substantially Ag-free and Zn-free, low density Al-Li alloy suitable for making transportation components, such as aerospace structural components.
  • Aluminum-lithium alloys of the present invention comprise from 3.6 to 4.1 wt. % Cu, 0.8 to 1.05 wt. % Li, 0.6 to 1.0 wt. % Mg, 0.2 to 0.6 wt. % Mn, up to 0.12 wt. % Si, up to 0.15 wt. % Fe, from 0.03 to 0.16 wt. % of at least one grain structure control element selected from the group consisting of Zr, Sc, Cr, V, Hf, and other rare earth elements, up to 0.10 wt.
  • % Ti up to 0.15 wt. % incidental elements with the total of incidental elements not exceeding 0.35 wt. %, and the balance being aluminum.
  • Ag is not intentionally added and should not be more than 0.05 wt. % as a non-intentionally added element.
  • Zn is not intentionally added and should not be more than 0.2 wt. % as a non-intentionally added element.
  • the amount of Cu in weight percent is at least equal to or higher than 4 times the amount of Li in weight percent in the inventive alloy.
  • the inventive alloy has improved properties over the prior art.
  • the inventive alloy has a tensile yield strength (TYS) along rolling (L) direction as function of plate gage (ga) that is higher than 75.0-1.4*ga, preferably higher than 76.2-1.4*ga, and more preferably higher than 77.0-1.4*ga.
  • the inventive alloy has a tensile yield strength (TYS) along long transverse (LT) direction that is higher than 71.2-1.4*ga, preferably higher than 72.2-1.4*ga, and more preferably higher than 72.7-1.4*ga.
  • the inventive alloy has a fracture toughness (K1c) along the orientation of Long Transverse - Rolling (T-L) that is higher than 28-1.0*ga, preferably higher than 29-1.0*ga, and more preferably higher than 29.5-1.0*ga.
  • the inventive alloy has a fracture toughness (K1c) along the orientation of Rolling - Long Transverse (L-T) that is higher than 28.8-0.6*ga, preferably higher than 30.8-0.6*ga, and more preferably higher than 31.8-0.6*ga.
  • the units for gage (ga), strength, and fracture toughness are inch, ksi, and ksi*in 1/2 respectively.
  • the aluminum-lithium alloy of the present invention is a plate, extrusion or forged wrought product having a thickness of 1.27 to 20.32 cm (0.5 to 8.0 inch). It has been surprisingly discovered that the aluminum-lithium alloy of the present invention having no Ag, or very low amounts of non- intentionally added Ag, no Zn, or very low amounts of non-intentionally added Zn, and high Mg content is capable of producing 1.27 to 20.32 cm (0.5 to 8.0 inch) thickness plate products with excellent strength and fracture toughness properties and desirable corrosion resistance performance. Another aspect of the present invention is a method to manufacture aluminum-lithium alloys of the present invention, set forth in Claim 12 of the accompanying claims.
  • the present invention is directed to aluminum-lithium alloys, specifically aluminum - copper - lithium - magnesium - manganese alloys.
  • the aluminum-lithium alloy of the present invention comprises from 3.6 to 4.1 wt. % Cu, 0.8 to 1.05 wt. % Li, 0.6 to 1.0 wt. % Mg, 0.2 to 0.6 wt. % Mn, up to 0.12 wt. % Si, up to 0.15 wt. % Fe, from 0.03 to 0.16 wt. % of at least one grain structure control element selected from the group consisting of Zr, Sc, Cr, V, Hf, and other rare earth elements, up to 0.10 wt. % Ti, up to 0.15 wt.
  • % incidental elements with the total of incidental elements not exceeding 0.35 wt. %, and the balance being aluminum.
  • Ag is not intentionally added and should not be more than 0.05 wt. % as a non-intentionally added element.
  • Zn is not intentionally added and should not be more than 0.2 wt. % as a non-intentionally added element.
  • the amount of Cu in weight percent is at least equal to or higher than 4 times the amount of Li in weight percent in the inventive alloy.
  • the aluminum-lithium alloy comprises from 3.7 to 4.0 wt. % Cu, 0.9 to 1.0 wt. % Li, 0.7 to 0.9 wt. % Mg along with 0.2 to 0.6 wt. % Mn, up to 0.12 wt. % Si, up to 0.15 wt. % Fe, from 0.03 to 0.16 wt. % of at least one grain structure control element selected from the group consisting of Zr, Sc, Cr, V, Hf, and other rare earth elements, up to 0.10 wt. % Ti, up to 0.15 wt. % incidental elements with the total of incidental elements not exceeding 0.35 wt. %, and the balance being aluminum.
  • Ag is not intentionally added and should not be more than 0.05 wt. % as a non-intentionally added element.
  • Zn is not intentionally added and should not be more than 0.2 wt. % as a non-intentionally added element.
  • the amount of Cu in weight percent is at least equal to or higher than 4 times the amount of Li in weight percent in the inventive alloy.
  • the aluminum-lithium alloy of the present invention can be used to produce wrought products, having a thickness range of 1.27 to 20.32 cm (0.5 - 8.0 inch).
  • the aluminum-lithium alloys of the present invention are wrought products having high strength, stronger damage tolerance, and excellent fatigue and corrosion resistance properties.
  • Such products are suitable for use in many structural applications, especially for aerospace structural components such as spar, rib, and integrally machined structural parts.
  • the aluminum-lithium alloy of the present invention can be used for the fabrication of components using several manufacturing processes such as high speed machining.
  • Copper is added to the aluminum-lithium alloy in the present invention in the range of 3.6 to 4.1 wt. %, mainly to enhance the strength but also to improve the combination of strength and fracture toughness.
  • An excessive amount of Cu can result in unfavorable intermetallic particles which can negatively affect material properties such as ductility and fracture toughness. In these cases the interaction of Cu with other elements such as Li and Mg must also be considered.
  • the upper or lower limit for the amount of Cu may be selected from 3.6, 3.7, 3.8, 3.9, 4.0, and 4.1 wt. %.
  • the Cu is from 3.7 to 4.0 wt. % to provide compositions that enhance specific product performance while maintaining relatively high performance in the remaining attributes as compared to the prior art.
  • Lithium is added to the aluminum-lithium alloy in the present invention in the range of 0.8 to 1.05 wt. %.
  • the primary benefit for adding Li is to reduce the density and increase the elastic modulus.
  • Li is critical in improving the strength, damage tolerance and corrosion performance. Li contents that are too high, however, can negatively impact fracture toughness, and anisotropy of tensile properties.
  • the present invention includes the alternative embodiments wherein the upper or lower limit for the amount of Li may be selected from 0.8, 0.9, 1.0, and 1.05 wt. %. In one preferred embodiment, Li is in the range of 0.9 to 1.0 wt. %.
  • the Cu/Li ratio significantly affects the desirable T1 strengthening phase, which is critical for strength, fracture toughness, and anisotropy of tensile properties.
  • the present invention requires the Cu/Li ratio should be higher than 4.0 in terms of wt. % Cu / wt. % Li.
  • Mg is added to the aluminum-lithium alloy in the present invention in the range of 0.6 to 1.0 wt. %.
  • the primary purpose of adding Mg is to enhance the strength with the secondary purpose of reducing the density.
  • Mg levels that are too high can reduce Li solubility in the matrix, thus negatively impacting the aging potential for higher strength.
  • the present invention includes alternative embodiments wherein the upper or lower limit for the amount of Mg may be selected from 0.6, 0.7, 0.8, 0.9, and 1.0 wt. %.
  • Mg is in the range of 0.7 to 0.9 wt. %.
  • Ag is not intentionally added in the aluminum-lithium alloy of the present invention.
  • Ag may exist in the alloy as a result of a non-intentional addition.
  • the Ag should not be more than 0.05 wt. %.
  • the present invention includes alternate embodiments wherein the upper or limit for the amount of Ag may be selected from 0.05, 0.04, 0.03, 0.02, and 0.01 wt.%
  • the prior art teaches that Ag is necessary to improve the final product properties and is therefore included in many aluminum-lithium alloys as well as many patents and patent applications. However, Ag significantly increases the cost of the alloys.
  • the aluminum-lithium alloy of the present invention Ag is not intentionally included in order to reduce the cost. It is surprising to find that the aluminum-lithium alloy of the present invention, without the addition of Ag for providing low cost, can be used to produce high strength, high fracture toughness, and excellent corrosion resistance plate products suitable for structural applications particularly in aerospace.
  • Zn can negatively affect the density and therefore Zn is not added in the present invention.
  • Zn may exist in the alloy as a result of a non-intentional addition. In this case, the Zn should not be more than 0.2 wt. %.
  • the present invention includes alternate embodiments having less than 0.15 wt. % Zn, less than 0.10 wt.% Zn, less than 0.05 wt.% Zn.
  • Mn is intentionally added to improve the grain structure for better mechanical isotropy and formability.
  • the present invention includes alternative embodiments wherein the upper or lower limits for the amounts of Mn may be selected from 0.2, 0.3, 0.4, 0.5, and 0.6 wt. %.
  • Ti can be added up to 0.10 wt. %.
  • the purpose of adding Ti is mainly for grain refinement in casting.
  • the present invention includes alternative embodiments wherein the upper limit for the amount of Ti may be selected from 0.01, 0.02, 0.05, 0.06, 0.07, 0.08, 0.09, and 0.10 wt. % Ti.
  • Si and Fe may be present in the aluminum-lithium alloy of the present invention as impurities but are not intentionally added.
  • the present invention includes alternate embodiments wherein the alloy includes ⁇ 0.12 wt. % for Si, and ⁇ 0.15 wt. % for Fe, preferably ⁇ 0.05 wt. % for Si and ⁇ 0.08 wt. % for Fe.
  • the aluminum-lithium alloy of the present invention includes a maximum content of 0.12 wt. % for Si, and 0.15 wt. % for Fe. In one preferred embodiment, the maximum contents are 0.05 wt. % for Si and 0.08 wt. % for Fe.
  • the aluminum-lithium alloy of the present invention may also include low levels of "incidental elements” that are not included intentionally.
  • the "incidental elements” means any other elements except Al, Cu, Li, Mg, Zr, Zn, Mn, Ag, Fe, Si, and Ti.
  • the low cost, high performance, high Mg content Al-Li alloy of the present invention may be used to produce wrought products.
  • the aluminum-lithium alloy of the present invention is capable of producing rolled products, preferably, a plate product in the thickness range of 1.27 to 20.32 cm (0.5 to 8.0 inch).
  • the upper or lower limit for the thickness may be selected from 1.27, 2.54, 5.08, 7.62, 10.16, 12.7, 15.24, 17.78 and 20.32 cm (0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0 and 8.0 inch).
  • the rolled products may be manufactured using known processes such as casting, homogenization, hot rolling, solution heat treating and quenching, stretching, and ageing treatments.
  • the ingot may be cast by traditional direct chill (DC) casting method.
  • the ingot may be homogenized at temperatures from 482 to 543°C (900 to 1010°F).
  • the hot rolling temperature may be from 357 to 482°C (675 to 900°F).
  • the products may be solution heat treated at temperature range of 482 to 538°C (900 to 1000°F).
  • the wrought products are cold water quenched to room temperature and may be stretched up to 15%, preferably from 2 to 8%.
  • the quenched and stretched product may be subjected to any aging practices known by those skilled in the art including, but not limited to, one-step aging practices that produce a final desirable temper, such as T8 temper, for better combination of strength, fracture toughness, and corrosion resistance which are highly desirable for aerospace members.
  • the aging temperature can be in the range of 121 to 205°C (250 to 400°F) and preferably from 149 to 182°C (300 to 360°F) and the aging time can be in the range of 2 to 60 hours, preferably from 10 to 48 hours.
  • the unique chemistry along with proper processing of present patent application results in plate products with surprising novel and basic material characteristics.
  • the tensile yield strength (TYS) along rolling (L) direction as function of plate gage (ga) is higher than 75.0-1.4*ga, preferably higher than 76.2-1.4*ga, and more preferably higher than 77.0-1.4*ga.
  • the tensile yield strength (TYS) along long transverse (LT) direction is higher than 71.2-1.4*ga, preferably higher than 72.2-1.4*ga, and more preferably higher than 72.7-1.4*ga.
  • the fracture toughness (K1c) along the orientation of Long Transverse - Rolling (T-L) is higher than 28-1.0*ga, preferably higher than 29-1.0*ga, and more preferably higher than 29.5-1.0*ga.
  • the fracture toughness (K1c) along the orientation of Rolling - Long Transverse (L-T) is higher than 28.8-0.6*ga, preferably higher than 30.8-0.6*ga, and more preferably higher than 31.8-0.6*ga.
  • the units for gage (ga), strength, and fracture toughness are inch, ksi, and ksi*in 1/2 respectively.
  • Table 1 gives the chemical compositions and final plate thickness. There are three groups: (1) “Invention”, (2) “Non-Invention (Substantially Ag-free)” and (3) “Non-Invention (Ag)".
  • the third group is obviously not the invention alloy due to the high cost Ag element and/or along with other conditions that do not meet invention alloy chemical composition limits.
  • samples are not invention alloys due to the combination of Cu/Li ratio, Cu, Li, and Zn limits.
  • the Cu/Li ratios for sample 12, 13 14, and 16 are lower than 4.0.
  • the Cu contents in sample 13 and 15 are lower than 3.6 wt. %.
  • the Li content in Sample 13 is higher than 1.05 wt. %.
  • the Zn content in Sample 16 is higher than 0.2 wt. %.
  • the ingots were homogenized at temperatures from 496 to 538°C (925 to 1000°F).
  • the hot rolling temperatures were from 371 to 466°C (700 to 870°F).
  • the ingots were hot rolled at multiple passes into 1" to 6" thickness.
  • the rolled plates were solution heat treated at a temperature range from 493 to 532°C (920 to 990°F).
  • the plates were cold water quenched to room temperature. All example plates were stretched by 2 to 7% in terms of plastic strain.
  • the stretched plates were further aged to T8 temper for strength, fracture, fatigue resistance, and corrosion resistance performance evaluation.
  • the aging temperature was from 160°C (320°F) to 171°C (340°F) for 8 to 70 hours.
  • the strength and fracture toughness as a function of aging process is one critical characteristic for alloy performance.
  • the selected substantially Ag-free addition 3" invention and non-invention alloy plates were evaluated under 166°C (330°F) aging temperature at different aging times.
  • Table 2 gives the tensile and fracture toughness testing results.
  • Tensile in LT direction at quarter thickness (T/4) was conducted under ASTM B557 specification.
  • the plane strain fracture toughness (K1c) in T-L orientations at middle thickness (T/2) was measured under ASTM E399 using CT specimens.
  • invention alloys have much faster / better strength response as aging time increases than non-invention alloys.
  • Such significant difference is mainly due to the distinctive chemical composition difference between invention alloys and non-invention alloys.
  • the desired aging practice with balanced strength and fracture toughness was selected for production aging treatment.
  • the production aged plates were comprehensively evaluated for tensile, fracture, corrosion and fatigue resistance.
  • Table 3 and 4 give the tensile properties along L, LT, and L45 (45° off the rolling direction) directions at quarter thickness (T/4) and middle thickness (T/2) for all production aged plates.
  • Table 5 gives the fracture toughness at the orientations of L-T, T-L and S-L at quarter thickness (T/4) and middle thickness (T/2) for all production aged plates.
  • Table 3 to 5 shows that the low cost invention alloy with unique chemical composition has surprisingly better material properties in terms of the combination of strength and fracture toughness.
  • FIG. 2 gives the comparison of LT TYS strength and K1c T-L fracture toughness between substantially Ag-free invention alloys and Non-invention alloys (No Ag) of 3 inch plates.
  • the invention alloys have a better combination of strength and fracture toughness.
  • the minimum LT TYS can be 67 ksi and minimum K1c T-L can be 25 ksi*in 1/2 for 3" plate.
  • the minimum LT TYS can be 68 ksi and minimum K1c T-L can be 26 ksi*in 1/2 for 3" plate.
  • the minimum LT TYS can be 68.5 ksi and minimum K1c T-L can be 26.5 ksi*in 1/2 for 3" plate.
  • the similar distinctiveness can be demonstrated in FIG. 3 for 3" L TYS and K1c L-T properties.
  • the minimum L TYS can be 70.8 ksi and minimum K1c L-T can be 27 ksi*in 1/2 for 3" plate.
  • the minimum L TYS can be 72.0 ksi and minimum K1c L-T can be 29 ksi*in 1/2 for 3" plate.
  • the minimum L TYS can be 72.8 ksi and minimum K1c L-T can be 30 ksi*in 1/2 for 3" plate.
  • FIG. 4 and 5 gives the comparison of LT TYS vs. K1c T-L and L TYS vs. K1c L-T between low cost substantially Ag-free invention alloys and high cost Ag containing non-invention alloys of 3 inch plates. It surprisingly shows that there is no significant difference between Ag containing non invention alloys and substantially Ag-free invention alloys in terms of the combination of strength and fracture toughness.
  • FIG. 6 to 9 gives the strength and fracture toughness as a function of plate thickness for invention alloy plates.
  • the tensile yield strength (TYS) along long transverse (LT) direction is higher than 71.2-1.4*ga, preferably higher than 72.2-1.4*ga, and more preferably higher than 72.7-1.4*ga.
  • the tensile yield strength (TYS) along rolling (L) direction as function of plate gage (ga) is higher than 75.0-1.4*ga, preferably higher than 76.2-1.4*ga, and more preferably higher than 77.0-1.4*ga.
  • the fracture toughness (K1c) along the orientation of Long Transverse - Rolling (T-L) is higher than 28-1.0*ga, preferably higher than 29-1.0*ga, and more preferably higher than 29.5-1.0*ga.
  • the fracture toughness (K1c) along the orientation of Rolling - Long Transverse (L-T) is higher than 28.8-0.6*ga, preferably higher than 30.8-0.6*ga, and more preferably higher than 31.8-0.6*ga.
  • the units for gage (ga), strength, and fracture toughness are inch, ksi, and ksi*in 1/2 respectively.
  • Corrosion resistance is a key design consideration for airframe manufacturers.
  • the MASTMASSIS test is generally considered to be a good representative accelerated corrosion test method for Al-Li based alloys.
  • the MASTMASSIS test was based on ASTM G85-11 Annex-2 under dry-bottom conditions.
  • the sample size was 4.5" L x 4.5" LT at middle of sheet thickness.
  • the temperature of the exposure chamber through the duration of the test was 49 ⁇ 2°C.
  • the testing through thickness location is T/2 (center of thickness).
  • the testing plane is L-LT plane.
  • the testing duration times were 24, 48, 96, 168, 336, 504, and 672hrs.
  • FIG. 10 gives the typical surface appearances after 672 hours MASTMASSIS testing exposure times.
  • the left photo is from invention alloy Sample #6 with 3 inch plate thickness and right photo is from invention alloy Sample #11 with 6 inch plate thickness.
  • the tested surfaces are very clean and shiny. No exfoliation is evident for all the exposure times. The excellent corrosion resistance of pitting/EA can be concluded for all exposure times for all invention alloy plates.
  • Stress corrosion cracking (SCC) resistance is also critical for aerospace application.
  • the standard stress corrosion cracking resistance testing was performed in accordance with the requirements of ASTM G47 which is alternate immersion in a 3.5% NaCl solution under constant deflection. Three specimens were tested per sample. The stress levels are 45 ksi and 50 ksi.
  • Table 6 gives the SCC testing results for Sample 6, 7, 8, 10 with final production ageing treatment. All specimens survived 30 days testing without failures under 45 ksi or 50 ksi stress levels in ST direction. Table 6: The SCC testing results for Sample 6, 7, 8, 10 with final production ageing treatment Sample ID Lot Gage, in Stress Repeat 1 Repeat 2 Repeat 3 6 187292B8 3.0 45 >30days >30days >30days >30days 7 652929A1 3.0 45 >30days >30days >30days >30days 7 652929A1 3.0 45 >30days >30days >30days >30days 8 187267B0 3.2 50 >30days >30days >30days >30days 10 130369B2 6.0 45 >30days >30days >30days >30days >30days >30days >30days >30days >30days.
  • the fatigue property was tested in accordance with the requirements of ASTM E466.
  • Four LT smooth specimens were tested from each plate at plate thickness center along long transverse (LT) direction.
  • Specimen was tested at 240MPa (35 ksi).
  • Table 7 gives the fatigue testing results of invention alloy plates.
  • the majority of fatigue test specimens had no failures after 300,000 cycles and all plates met the common industrially accepted criterion, i.e. 120,000 cycles of logarithm average of four specimens.
  • Table 7 The smooth fatigue testing results of invention alloy plates Sample ID Lot # Gage, in Specimen-1 Specimen-2 Specimen-3 Specimen-4 Log Average 1 130432B8 1 >300,000 >300,000 >300,000 >300,000 >300,000 >300,000 2 130408B8 2 >300,000 >300,000 >300,000 >300,000 3 130275B1 3 >300,000 >300,000 >300,000 >300,000 >300,000 4 130285B0 3 >300,000 >300,000 >300,000 >300,000 >300,000 >300,000 5 18741380 3 >300,000 >300,000 >300,000 >300,000 >300,000 >300,000 6 187292B8 3 >300,000 >300,000 >300,000 >300,000 >300,000 >300,000 7 652929A1 3 289,683 196,242 244,917 >300,000 >254,222 8 187267B0 3.2 >300,000
  • the material performance is strongly related to material grain structure, which is greatly affected by alloy chemical composition along with thermal mechanical processing procedure. Specifically for Al-Li plate products, an unrecrystallized grain structure is desirable for better strength, fracture toughness and corrosion resistance performance.
  • FIG. 11 to 15 gives the grain structures of different thickness invention alloy plates. All the invention alloy plates have unrecrystallized grain structures at both quarter thickness (T/4) and middle thickness (T/2).

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)
  • Metal Rolling (AREA)

Claims (13)

  1. Alliage d'aluminium et de lithium à haute résistance, de faible densité et à faible coût comprenant :
    de 3,6 % à 4,1 % en poids de Cu, de 0,8 % à 1,05 % en poids de Li,
    de 0,6 % à 1,0 % en poids de Mg, de 0,2 % à 0,6 % en poids de Mn,
    moins de 0,05 % en poids de Ag, moins de 0,2 % en poids de Zn,
    de 0,03 % à 0,16 % en poids d'au moins un élément de contrôle de la structure des grains choisi dans le groupe constitué de Zr, de Sc, de Cr, de V, de Hf et
    d'autres éléments des terres rares,
    jusqu'à 0,10 % en poids de Ti,
    jusqu'à 0,12 % en poids de Si,
    jusqu'à 0,15 % en poids de Fe,
    jusqu'à 0,15 % en poids chacun d'éléments aléatoires, le total des éléments aléatoires ne dépassant pas 0,35 % en poids, dans lequel les éléments aléatoires ne sont pas inclus de manière intentionnelle et dans lequel les éléments aléatoires comprennent tous les éléments à l'exception de Al, de Cu, de Li, de Mg, de Zr, de Zn, de Mn, de Ag, de Fe, de Si, et de Ti,
    le reste étant de l'aluminium, et
    dans lequel la quantité de Cu en pourcentage massique est au moins égale ou
    supérieure à quatre fois la quantité de Li en pourcentage massique.
  2. Alliage d'aluminium et de lithium selon la revendication 1, comprenant de 3,7 à 4,0 % en poids de Cu.
  3. Alliage d'aluminium et de lithium selon la revendication 1 ou 2, comprenant de 0,9 à 1,0 % en poids de Li.
  4. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 3, comprenant de 0,7 à 0,9 % en poids de Mg.
  5. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 4, dans lequel pas de Ag est intentionnellement ajouté à l'alliage d'aluminium.
  6. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 5, dans lequel pas de Zn est intentionnellement ajouté à l'alliage d'aluminium.
  7. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 5, comprenant moins de 0,10 % en poids de Zn ;
    comprenant éventuellement moins de 0,05 % en poids de Zn.
  8. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 7, comprenant un maximum de 0,05 % en poids de Si ;
    et/ou
    comprenant un maximum de 0,08 % en poids de Fe.
  9. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 8, comprenant :
    de 3,7 % à 4,0 % en poids de Cu, de 0,9 % à 1,0 % en poids de Li,
    de 0,7 % à 0,9 % en poids de Mg, de 0,2 % à 0,6 % en poids de Mn,
    moins de 0,05 % en poids de Ag, moins de 0,2 % en poids de Zn,
    de 0,03 % à 0,16 % en poids d'au moins un élément de contrôle de la structure des grains choisi dans le groupe constitué de Zr, de Sc, de Cr, de V, de Hf et
    d'autres éléments des terres rares,
    jusqu'à 0,10 % en poids de Ti,
    jusqu'à 0,12 % en poids de Si,
    jusqu'à 0,15 % en poids de Fe,
    jusqu'à 0,15 % en poids chacun d'éléments aléatoires, le total de ces éléments aléatoires ne dépassant pas 0,35 % en poids, dans lequel les éléments aléatoires ne sont pas inclus de manière intentionnelle et dans lequel les éléments aléatoires comprennent tous les éléments à l'exception de Al, de Cu, de Li, de Mg, de Zr, de Zn, de Mn, de Ag, de Fe, de Si, et de Ti,
    le reste étant de l'aluminium, et
    dans lequel la quantité de Cu en pourcentage massique est au moins égale ou
    supérieure à quatre fois la quantité de Li en pourcentage massique
  10. Alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 9, dans lequel ledit alliage d'aluminium et de lithium se trouve sous la forme d'un produit laminé, extrudé ou forgé, et a une épaisseur allant de 1,27 à 20,32 cm (de 0,5 à 8,0 pouces).
  11. Alliage d'aluminium et de lithium selon la revendication 10, dans lequel ledit alliage d'aluminium et de lithium a une épaisseur allant de 1,27 à 15,24 cm (de 0,5 à 6,0 pouces).
  12. Procédé de fabrication d'un alliage d'aluminium et de lithium à haute résistance, de faible densité et à faible coût, le procédé comprenant :
    a. le moulage de stock d'un lingot de l'alliage d'aluminium comprenant le produit d'alliage d'aluminium et de lithium selon l'une quelconque des revendications 1 à 11 afin de produire un stock de fonte ;
    b. l'homogénéisation du stock de fonte afin de produire un stock de fonte homogénéisé ;
    c. le travail à chaud du stock de fond homogénéisé par l'un ou plusieurs procédés choisis dans le groupe constitué par le laminage, l'extrusion et le forgeage permettant de former un stock travaillé ;
    d. le traitement thermique de mise en solution (SHT) du stock travaillé afin de produire un stock de SHT ;
    e. la trempe à l'eau froide dudit stock de SHT afin de produire un stock de SHT trempé à l'eau froide ;
    f. l'étirage du stock de SHT trempé à l'eau froide afin de produire un stock étire ; et
    g. le vieillissement artificiel du stock étiré.
  13. Procédé selon la revendication 12, dans lequel ladite étape d'homogénéisation inclut l'homogénéisation à des températures allant de 482 à 543 °C (de 900 à 1010 °F) ; dans lequel ladite étape de travail à chaud comprend un laminage à chaud à une température allant de 357 à 482 °C (de 675 à 900 °F) ; dans lequel ladite étape de traitement thermique de mise en solution comprend le traitement thermique de mise en solution dans une plage de températures allant de 482 à 538 °C (de 900 à 1000 °F) ; dans lequel ladite étape d'étirage comprend un étirage allant de 2 à 15 % ; dans lequel ladite étape de vieillissement artificiel comprend le vieillissement à une température allant de 121 à 205 °C (de 250 à 400 °F) et le temps de vieillissement peut être compris dans la plage allant de 2 à 60 heures,
    dans lequel, éventuellement, ladite étape de vieillissement artificiel comprend le vieillissement à une température allant de 149 à 182 °C (de 300 à 360 °F) et le temps de vieillissement peut être compris dans la plage allant de 10 à 48 heures.
EP19155140.7A 2018-02-01 2019-02-01 Alliage de plaque d'aluminium-lithium à faible densité, à faible coût, essentiellement exempt d'ag et de zn, pour application aérospatiale Active EP3521467B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/886,189 US20190233921A1 (en) 2018-02-01 2018-02-01 Low Cost, Low Density, Substantially Ag-Free and Zn-Free Aluminum-Lithium Plate Alloy for Aerospace Application

Publications (2)

Publication Number Publication Date
EP3521467A1 EP3521467A1 (fr) 2019-08-07
EP3521467B1 true EP3521467B1 (fr) 2020-10-21

Family

ID=65351866

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19155140.7A Active EP3521467B1 (fr) 2018-02-01 2019-02-01 Alliage de plaque d'aluminium-lithium à faible densité, à faible coût, essentiellement exempt d'ag et de zn, pour application aérospatiale

Country Status (4)

Country Link
US (1) US20190233921A1 (fr)
EP (1) EP3521467B1 (fr)
CN (1) CN110106409A (fr)
ES (1) ES2834134T3 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3947761A4 (fr) * 2019-04-05 2022-11-30 Arconic Technologies LLC Procédés de formage à froid d'alliages d'aluminium-lithium
CN110791720B (zh) * 2019-11-25 2020-11-24 重庆文理学院 一种抑制铝锂合金再结晶的加工方法
CN114855039B (zh) * 2021-02-03 2023-06-23 中国石油化工股份有限公司 一种Al-Cu-Mg-Ag合金及其制备方法和应用
CN113215423B (zh) * 2021-04-16 2022-07-08 中南大学 一种高强度耐损伤铝锂合金及其制备方法和应用
US12203159B2 (en) 2021-04-23 2025-01-21 Universal Alloy Corporation Method for producing aluminum-copper alloys containing scandium
CN115842206B (zh) * 2022-02-10 2024-08-16 宁德时代新能源科技股份有限公司 一种锂离子电池用铝合金板材及电池壳体
CN120249707B (zh) * 2025-04-02 2025-12-09 佛山市璟熙金属制品有限公司 一种耐磨抗氧化锂铝合金的制备方法

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5137686A (en) * 1988-01-28 1992-08-11 Aluminum Company Of America Aluminum-lithium alloys
US4961792A (en) * 1984-12-24 1990-10-09 Aluminum Company Of America Aluminum-lithium alloys having improved corrosion resistance containing Mg and Zn
US4915747A (en) * 1985-10-31 1990-04-10 Aluminum Company Of America Aluminum-lithium alloys and process therefor
US4921548A (en) * 1985-10-31 1990-05-01 Aluminum Company Of America Aluminum-lithium alloys and method of making same
US4816087A (en) * 1985-10-31 1989-03-28 Aluminum Company Of America Process for producing duplex mode recrystallized high strength aluminum-lithium alloy products with high fracture toughness and method of making the same
FR2626009B2 (fr) * 1987-02-18 1992-05-29 Cegedur Produit en alliage d'al contenant du li resistant a la corrosion sous tension
US5122339A (en) * 1987-08-10 1992-06-16 Martin Marietta Corporation Aluminum-lithium welding alloys
US5066342A (en) * 1988-01-28 1991-11-19 Aluminum Company Of America Aluminum-lithium alloys and method of making the same
US4869870A (en) * 1988-03-24 1989-09-26 Aluminum Company Of America Aluminum-lithium alloys with hafnium
US5455003A (en) * 1988-08-18 1995-10-03 Martin Marietta Corporation Al-Cu-Li alloys with improved cryogenic fracture toughness
US5211910A (en) * 1990-01-26 1993-05-18 Martin Marietta Corporation Ultra high strength aluminum-base alloys
US7438772B2 (en) * 1998-06-24 2008-10-21 Alcoa Inc. Aluminum-copper-magnesium alloys having ancillary additions of lithium
FR2789406B1 (fr) * 1999-02-04 2001-03-23 Pechiney Rhenalu PRODUIT EN ALLIAGE AlCuMg POUR ELEMENT DE STRUCTURE D'AVION
FR2802946B1 (fr) * 1999-12-28 2002-02-15 Pechiney Rhenalu Element de structure d'avion en alliage al-cu-mg
US20030226935A1 (en) * 2001-11-02 2003-12-11 Garratt Matthew D. Structural members having improved resistance to fatigue crack growth
FR2842212B1 (fr) * 2002-07-11 2004-08-13 Pechiney Rhenalu Element de structure d'avion en alliage a1-cu-mg
US7323068B2 (en) * 2002-08-20 2008-01-29 Aleris Aluminum Koblenz Gmbh High damage tolerant Al-Cu alloy
US7604704B2 (en) * 2002-08-20 2009-10-20 Aleris Aluminum Koblenz Gmbh Balanced Al-Cu-Mg-Si alloy product
CN101189353A (zh) * 2005-06-06 2008-05-28 爱尔康何纳吕公司 用于飞机机身的高韧度的铝-铜-锂合金板材
FR2925523B1 (fr) * 2007-12-21 2010-05-21 Alcan Rhenalu Produit lamine ameliore en alliage aluminium-lithium pour applications aeronautiques
US7811395B2 (en) * 2008-04-18 2010-10-12 United Technologies Corporation High strength L12 aluminum alloys
US7875133B2 (en) * 2008-04-18 2011-01-25 United Technologies Corporation Heat treatable L12 aluminum alloys
FR2947282B1 (fr) * 2009-06-25 2011-08-05 Alcan Rhenalu Alliage aluminium cuivre lithium a resistance mecanique et tenacite ameliorees
FR2981365B1 (fr) * 2011-10-14 2018-01-12 Constellium Issoire Procede de transformation ameliore de toles en alliage al-cu-li
FR2989387B1 (fr) * 2012-04-11 2014-11-07 Constellium France Alliage aluminium cuivre lithium a resistance au choc amelioree
US9458528B2 (en) * 2012-05-09 2016-10-04 Alcoa Inc. 2xxx series aluminum lithium alloys
FR3004197B1 (fr) * 2013-04-03 2015-03-27 Constellium France Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion.
FR3004196B1 (fr) * 2013-04-03 2016-05-06 Constellium France Toles en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion.
FR3004464B1 (fr) * 2013-04-12 2015-03-27 Constellium France Procede de transformation de toles en alliage al-cu-li ameliorant la formabilite et la resistance a la corrosion
FR3014448B1 (fr) * 2013-12-05 2016-04-15 Constellium France Produit en alliage aluminium-cuivre-lithium pour element d'intrados a proprietes ameliorees
FR3014904B1 (fr) * 2013-12-13 2016-05-06 Constellium France Produits files pour planchers d'avion en alliage cuivre lithium
FR3014905B1 (fr) * 2013-12-13 2015-12-11 Constellium France Produits en alliage d'aluminium-cuivre-lithium a proprietes en fatigue ameliorees
US10253404B2 (en) * 2014-10-26 2019-04-09 Kaiser Aluminum Fabricated Products, Llc High strength, high formability, and low cost aluminum-lithium alloys
US20180305795A1 (en) * 2015-11-25 2018-10-25 Otto Fuchs Kommanditgesellschaft Tube for Use in Conjunction with a Deep Drilled Hole
FR3047253B1 (fr) * 2016-02-03 2018-01-12 Constellium Issoire Toles epaisses en alliage al - cu - li a proprietes en fatigue ameliorees
CN109072358A (zh) * 2016-02-09 2018-12-21 爱励轧制产品德国有限责任公司 Al-Cu-Li-Mg-Mn-Zn合金锻制产品
US20180291489A1 (en) * 2017-04-11 2018-10-11 The Boeing Company Aluminum alloy with additions of copper, lithium and at least one alkali or rare earth metal, and method of manufacturing the same
US20190169727A1 (en) * 2017-12-04 2019-06-06 Kaiser Aluminum Fabricated Products, Llc Low Cost, Substantially Zr-Free Aluminum-Lithium Alloy for Thin Sheet Product with High Formability

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
EP3521467A1 (fr) 2019-08-07
US20190233921A1 (en) 2019-08-01
ES2834134T3 (es) 2021-06-16
CN110106409A (zh) 2019-08-09

Similar Documents

Publication Publication Date Title
EP3521467B1 (fr) Alliage de plaque d'aluminium-lithium à faible densité, à faible coût, essentiellement exempt d'ag et de zn, pour application aérospatiale
EP2049696B1 (fr) Alliage d'aluminium à haute résistance pouvant être traité thermiquement
EP0584271B1 (fr) ALLIAGE DE Al-Li A RESISTANCE ELEVEE ET A FAIBLE DENSITE
EP2558564B1 (fr) Alliages d'aluminium lithium de série 2xxx à faible différentiel de résistance
US8608876B2 (en) AA7000-series aluminum alloy products and a method of manufacturing thereof
RU2404276C2 (ru) ПРОДУКТ ИЗ ВЫСОКОПРОЧНОГО, ВЫСОКОВЯЗКОГО Al-Zn СПЛАВА И СПОСОБ ИЗГОТОВЛЕНИЯ ТАКОГО ПРОДУКТА
EP1861516B1 (fr) Alliages a base d'aluminium al-zn-cu-mg et procedes de production et d'utilisation
EP3012338B1 (fr) Alliages d'aluminium lithium à faible coût, à résistance élevée et grande formabilité
US20070258847A1 (en) NEW Al-Cu-Li-Mg-Ag-Mn-Zr ALLOY FOR USE AS STRUCTURAL MEMBERS REQUIRING HIGH STRENGTH AND HIGH FRACTURE TOUGHNESS
EP1945825B1 (fr) Alliages a base d'aluminium, de cuivre et de magnesium (al cu mg) pour les applications aerospatiales
EP2847361B1 (fr) Alliages d'aluminium lithium de série 2xxx
JP3540812B2 (ja) 高温で高靭性を有する低密度高強度のアルミニウム−リチウム合金
EP2662467A1 (fr) Produits en alliage d'aluminium de série 7xxx ultra épais à résistance élevée et procédés de fabrication de tels produits
KR20210078537A (ko) 7xxx-시리즈 알루미늄 합금 제품
KR102547038B1 (ko) 피로 파괴 내성이 개선된 7xxx-시리즈 알루미늄 합금 판 제품의 제조 방법
US20210207254A1 (en) Al-Cu-Li-Mg-Mn-Zn ALLOY WROUGHT PRODUCT
EP3495520B1 (fr) Alliage aluminium-lithium à faible coût et sensiblement sans zr pour un produit en feuille mince à haute formabilité
EP3101149A1 (fr) Produits en alliage d'aluminium de série 7xxx ultra épais à haute résistance et procédés de fabrication de tels produits
EP4001446A1 (fr) Produits en alliage aérospatial 7xxx à haute résistance et haute ténacité à la rupture
US20210262065A1 (en) 2xxx aluminum alloys
EP4155426A1 (fr) Produits en alliage dispersoides 7xxx avec résistance améliorée à la fissuration assistée par l'environnement et résistance à la déviation de la croissance de la fissure de fatigue
US20190368009A1 (en) High Strength, Better Fatigue Crack Deviation Performance, and High Anisotropic Ductility 7xxx Aluminum Alloy Products and Methods of Making Such Products
CN117881809A (zh) 生产2xxx铝合金的方法

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: THE APPLICATION HAS BEEN PUBLISHED

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

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: 20200207

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: 20200514

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: DE

Ref legal event code: R096

Ref document number: 602019000973

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: NOVAGRAAF INTERNATIONAL SA, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1325948

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201115

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20201021

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: 20210122

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: 20210121

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: 20201021

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: 20201021

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: 20210222

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: 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: 20210221

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: 20201021

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: 20201021

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: 20210121

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: 20201021

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2834134

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20210616

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

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: 20201021

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: 20201021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019000973

Country of ref document: DE

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: 20201021

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: 20201021

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: 20201021

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: 20201021

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: 20201021

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

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: 20201021

26N No opposition filed

Effective date: 20210722

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: 20201021

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: 20210201

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: 20201021

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: 20201021

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: 20210201

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: 20210221

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1325948

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201021

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

Ref country code: RO

Payment date: 20230125

Year of fee payment: 5

Ref country code: ES

Payment date: 20230317

Year of fee payment: 5

Ref country code: CH

Payment date: 20230307

Year of fee payment: 5

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

Ref country code: IT

Payment date: 20230228

Year of fee payment: 5

Ref country code: DE

Payment date: 20230216

Year of fee payment: 5

Ref country code: BE

Payment date: 20230220

Year of fee payment: 5

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

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: 20201021

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

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: 20190201

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: 20201021

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: 20201021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602019000973

Country of ref document: DE

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: 20201021

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: CH

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

Effective date: 20240229

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

Ref country code: RO

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

Effective date: 20240201

Ref country code: CH

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

Effective date: 20240229

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20240229

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

Ref country code: DE

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

Effective date: 20240903

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: 20240229

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

Ref country code: DE

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

Effective date: 20240903

Ref country code: BE

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

Effective date: 20240229

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 NON-PAYMENT OF DUE FEES

Effective date: 20240201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20250326

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

Ref country code: ES

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

Effective date: 20240202

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

Ref country code: AT

Payment date: 20250217

Year of fee payment: 7

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

Ref country code: FR

Payment date: 20250220

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20250210

Year of fee payment: 7