WO2023144492A1 - Tole mince amelioree en alliage d'aluminium-cuivre-lithium - Google Patents
Tole mince amelioree en alliage d'aluminium-cuivre-lithium Download PDFInfo
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- WO2023144492A1 WO2023144492A1 PCT/FR2023/050105 FR2023050105W WO2023144492A1 WO 2023144492 A1 WO2023144492 A1 WO 2023144492A1 FR 2023050105 W FR2023050105 W FR 2023050105W WO 2023144492 A1 WO2023144492 A1 WO 2023144492A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- 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
- 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
- C22C21/16—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
- 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 invention relates to thin aluminum-copper-lithium alloy sheets, more particularly, such products, their methods of manufacture and use, intended in particular for aeronautical and aerospace construction for fuselage sheet applications.
- Aluminum-lithium alloys are very interesting in this regard, because lithium can reduce the density of aluminum by 3% and increase the modulus of elasticity by 6% for each weight percent of lithium added.
- EP 1 891 247 discloses a low density aluminum-based alloy useful in an aircraft structure for fuselage sheet metal applications having high mechanical strength, high toughness and high corrosion resistance, containing in % by weight, 2.7 to 3.4 Cu, 0.8 to 1.4 Li, 0.1 to 0.8 Ag, 0.2 to 0.6 Mg and an element such as Zr, Mn, Cr, Sc, Hf, Ti or a combination thereof, the amount of which, in % by weight, is 0.05 to 0.13 for Zr, 0.05 to 0.8 for Mn, 0, 05 to 0.3 for Cr and Sc, 0.05 to 0.5 for Hf and 0.05 to 0.15 for Ti.
- the amount of Cu and Li is determined according to the formula Cu (% by weight) + 5/3 Li (% by weight) ⁇ 5.2.
- Fuselage sheets can be stressed in several directions and isotropic thin sheets having high and balanced properties in mechanical strength in the L and TL directions and in toughness for the LT and TL directions are highly sought after.
- thin sheets obtained with certain alloys having high properties at certain thicknesses for example 4 mm, can in certain cases have lower or anisotropic properties at another thickness, for example 2.5 mm. It is often not industrially advantageous to use different alloys for different thicknesses and an alloy making it possible to achieve high and isotropic properties regardless of the thickness would be particularly advantageous.
- Patent EP 1 966402 describes an alloy comprising 2.1 to 2.8% by weight of Cu, 1.1 to 1.7% by weight of Li, 01 to 0.8% by weight of Ag, 0.2 to 0.6% by weight of Mg, 0.2 to 0.6% by weight of Mn, an amount of Fe and Si less than or equal to 0.1% by weight each, and unavoidable impurities at a content less than or equal to 0.05% by weight each and 0.15% by weight in total, the alloy being substantially free of zirconium, particularly suitable for obtaining recrystallized thin sheets.
- W02016/051099 describes a 0.5 to 9 mm thick sheet of essentially recrystallized granular structure in aluminum-based alloy comprising 2.8 to 3.2% by weight of Cu, 0.5 to 0.8% in weight Li, 0.1-0.3 wt% Ag, 0.2-0.7 wt% Mg, 0.2-0.6 wt% Mn, 0.01-0.15 % by weight of Ti, an amount of Zn less than 0.2% by weight, an amount of Fe and Si less than or equal to 0.1% by weight each, and unavoidable impurities at a content less than or equal to 0 0.05% by weight each and 0.15% by weight in total, said sheet being obtained by a process comprising casting, homogenization, hot rolling and optionally cold rolling, solution treatment, quenching and tempering.
- WO2016/051099 discloses R-curve data in Figures 1 and 2. These R-curves are not limited to only valid points. The inventors have found that the disclosure of WO2016/051099, as well as the examples do not make it possible to obtain a value of Aaeff_max greater than 80 mm.
- Curve R represents the evolution of the critical effective stress intensity factor for crack propagation as a function of effective crack extension, under increasing monotonic stress. It allows the determination of the critical load for unstable failure for any configuration relevant to cracked aircraft structures.
- the values for stress intensity factor and crack extension are effective values as defined in ASTM E561-20.
- a first object of the invention is a thin sheet with a thickness of less than 12.7 mm, of essentially recrystallized granular structure in an aluminum-based alloy comprising, in% by weight, 2.5 to 3.5% of Cu, 0, 7-0.9% Li, 0.3-0.5% Mg, 0.2-0.5% Mn, 0.25-0.65% Zn, 0.01-0.15% of Ti, 0 to 0.07% of Ag, an amount of Fe and Si less than or equal to 0.1% each, and unavoidable impurities at a content less than or equal to 0.05% each and 0.15 % by weight in total, rest aluminum.
- a second object of the invention is a process for manufacturing a thin sheet with a thickness of less than 12.7 mm, in aluminum alloy in which, successively a) a bath of liquid metal is produced so as to obtain an alloy of aluminum comprising in% by weight, 2.5 to 3.5% Cu, 0.7 to 0.9% Li, 0.3 to 0.5% Mg, 0.2 to 0.5% Mn, 0.25 to 0.65% Zn,
- Yet another object of the invention is the use of a thin sheet according to the invention or obtained according to the method of the invention for fuselage structural elements.
- Figure 1 represents the evolution of the tensile yield strength Rp0.2 as a function of the tempering time at 155°C for different sheets according to example 1.
- Figure 2 represents the RpO.2-TL - Kapp (T-L) compromise of the sheets tested in examples 1 and 3.
- Figure 3 represents the compromise Rp0.2 -TL- Aaeff_max of the sheets tested in examples 1 and 3. Detailed description of the invention
- an essentially non-recrystallized granular structure is called a granular structure such that the recrystallization rate at % thickness is less than 30% and preferably less than 10% and an essentially recrystallized granular structure is called a granular structure such that the recrystallization rate at % thickness is greater than 70% and preferably greater than 90%.
- the recrystallization rate is defined as the fraction of area on a metallographic section occupied by recrystallized grains. Grain sizes are measured according to ASTM E112 -2013.
- the static mechanical characteristics in other words the ultimate breaking strength Rm, the tensile yield strength R p o,2 and the elongation at break A, are determined by a tensile test according to EN 6892-1-2019, the location from which the parts are taken and their direction being defined by EN 485-1-2016.
- a curve giving the effective stress intensity factor versus effective crack extension, known as the R-curve, is determined according to ASTM E 561-20.
- the critical stress intensity factor KC in other words the intensity factor that makes the crack unstable, is calculated from the R-curve.
- the stress intensity factor KCO is also calculated by assigning the length from initial crack at the beginning of the monotonic load, to the critical load. These two values are calculated for a specimen of the required shape.
- Kapp represents the KCO factor corresponding to the specimen that was used to perform the R-curve test.
- Keff represents the KC factor corresponding to the specimen that was used to perform the R-curve test.
- Aaeff_max represents the crack extension of the last valid point of the R-curve, valid according to ASTM E561-20.
- the crack size at the end of the pre-fatigue cracking stage is W/3 for type M(T) specimens, where W is the width of the specimen as defined in the ASTM standard E561-20.
- the width of the specimen used in a toughness test can have a substantial influence on the R-curve measured in the test. Since the fuselage sheets are large panels, only the toughness results obtained on sufficiently wide samples, such as samples having a width greater than or equal to 400 mm, are considered significant for the assessment of toughness. For this reason, only CCT760 test specimens, which have a width of 760 mm, were used for toughness evaluation.
- a fuselage structural element includes the elements that make up the fuselage such as the fuselage skin, the fuselage stiffeners or stringers, the bulkheads (bulkheads), the fuselage frames (circumferential frames ).
- sheet or “thin sheet” used interchangeably in this disclosure, it is meant a rolled product not exceeding 12.7 mm or 0.5 inch in thickness.
- the sheets according to the invention have a thickness comprised from 0.5 to 12.7 mm, preferentially from 0.5 mm to 9 mm, more preferentially from 1.5 mm to 6 mm.
- a selected class of aluminum alloys containing specific and critical amounts of copper, lithium, magnesium, zinc, manganese but containing essentially no silver makes it possible to prepare thin sheets having a improved compromise between toughness and mechanical resistance, and an improved Aaeff_max value corresponding to the crack extension of the last valid point of the R curve.
- the thin sheet with a thickness of less than 12.7 mm, of essentially recrystallized granular structure in aluminum-based alloy comprising wt%, 2.5-3.5% Cu, 0.7-0.9% Li, 0.3-0.5% Mg, 0.2-0.5% Mn, 0, 25 to 0.65% Zn, 0.01 to 0.15% Ti, 0 to 0.07% Ag, an amount of Fe and Si less than or equal to 0.1% each, and impurities unavoidable at a content less than or equal to 0.05% each and 0.15% in total, the remainder aluminum is in the T8 metallurgical state.
- the thin sheet has undergone solution treatment, cold deformation and tempering.
- the copper content is 2.5 to 3.5% by weight. If the copper content is more than 3.5% by weight, it is not possible to obtain sufficient toughness. Preferably, the copper content is at most 3.4%, 3.3%, 3.2% or 3.1%. If the copper content is less than 2.5% is too low. Preferably the copper content is at least 2.7% or even at least 2.8% by weight in order to obtain sufficient mechanical strength. In an advantageous embodiment of the invention, the copper content is 2.8 to 3.1% by weight.
- the lithium content is 0.7% to 0.9% by weight. In an advantageous embodiment of the invention, the lithium content is from 0.7% to 0.8%, preferably from 0.70 to 0.80%.
- the addition of lithium can contribute to the increase in the mechanical resistance and the toughness, a content that is too high or too low does not make it possible to obtain a high value of toughness and/or a sufficient elastic limit.
- the magnesium content is 0.3% to 0.5% by weight. In an advantageous embodiment of the invention, the magnesium content is from 0.30% to 0.45% by weight, preferably from 0.35% to 0.45% by weight.
- the manganese content is 0.2 to 0.5% by weight and preferably 0.20% to 0.45% by weight, and even more preferably 0.25% to 0.45% by weight . In one embodiment of the invention the manganese content is at most 0.45% by weight. Addition of manganese in the amount claimed controls the essentially recrystallized grain structure at mid-thickness while maintaining a homogeneous structure through the thickness.
- the silver content is less than or equal to 0.07% by weight, preferably less than or equal to 0.05% by weight, even more preferably less than or equal to 0.04% by weight, or even 0.03% by weight.
- the zinc content is 0.25 to 0.65% by weight, preferably 0.45% to 0.65% by weight. According to the present invention, it has been observed that the presence of zinc in the contents between 0.25% and 0.65% combined with a silver content less than or equal to 0.07% by weight, preferably less than or equal to 0.04% or even 0.03% makes it possible to obtain a higher tensile yield strength near the peak of tempering.
- the titanium content is 0.01% to 0.15% by weight.
- the titanium content is at least 0.02% by weight and preferably at least 0.03% by weight.
- the titanium content is at most 0.1% by weight and preferably at most 0.05% by weight.
- the addition of titanium helps to control the grain structure, especially during casting.
- the iron and silicon contents are each at most 0.1% by weight. In an advantageous embodiment of the invention, the iron and silicon contents are at most 0.08% and preferably at most 0.04% by weight.
- a controlled and limited iron and silicon content contributes to the improvement of the compromise between mechanical resistance and damage tolerance.
- the unavoidable impurities are maintained at a content less than or equal to 0.05% by weight each and 0.15% by weight in total.
- the rest is aluminum.
- the alloy composition is substantially free of zirconium.
- substantially free of zirconium is meant that zirconium is not an intentionally added addition element. It may however be present as impurities at a zirconium content of less than or equal to 0.05% by weight, preferably less than or equal to 0.04% by weight, even more preferably less than or equal to 0, 03% by weight, or even less than or equal to 0.01% by weight.
- the thin sheets according to the invention have in the T8 state:
- the sheet manufacturing process according to the invention comprises steps of production, casting, rolling, solution treatment, quenching, controlled traction and tempering.
- a bath of liquid metal is prepared so as to obtain an aluminum alloy of composition according to the invention.
- the liquid metal bath is then cast in a form of rolling plate.
- the rolling plate is then homogenized at a temperature between 480°C and 535° and preferably between 490°C and 530°C and preferably between 500°C and 520°C.
- the homogenization time is preferably between 5 and 60 hours. In the context of the invention, too low a homogenization temperature or the absence of homogenization does not make it possible to achieve improved and isotropic properties compared to those of known products, in particular in terms of mechanical resistance in the L and TL directions and toughness for the L-T and T-L directions, over the whole of this thickness range.
- the rolling plate After homogenization, the rolling plate is generally cooled to ambient temperature before being preheated in order to be hot deformed.
- the purpose of the preheating is to reach a temperature preferably between 400 and 500° C. allowing the deformation by hot rolling.
- the hot and optionally cold rolling is carried out so as to obtain a sheet with a thickness of less than 12.7 mm, preferably between 0.5 and 9 mm.
- a temperature above 400° C., preferably above 450° C. is maintained up to a thickness of 20 mm.
- Intermediate heat treatments during rolling and/or after rolling can be carried out in certain cases.
- the method does not include any intermediate heat treatment during rolling and/or after rolling.
- the sheet thus obtained is then dissolved by heat treatment between 450 and 535°C, preferably between 490°C and 530°C and preferably between 500°C and 520°C, preferably for 5 min to 2 hours. , then soaked.
- the dissolution time is at most 1 hour so as to minimize surface oxidation. It is known to those skilled in the art that the precise conditions for placing solution must be chosen according to the thickness and the composition so as to put the hardening elements in solid solution.
- the sheet then undergoes cold deformation by controlled traction with a permanent deformation of 0.5 to 5% and preferably of 1 to 3%.
- Known steps such as rolling, planing, smoothing, straightening shaping can optionally be carried out after solution treatment and quenching and before or after controlled traction, however total cold deformation after solution treatment and quenching must remain below 15% and preferably below 10%.
- Tempering is carried out comprising heating at a temperature of between 130 and 170° C. and preferably between 150 and 160° C. for 5 to 100 hours and preferably from 10 to 40 hours.
- the tempering treatment is carried out in such a way as to obtain an equivalent duration t1 eq at 150° C. comprised from 10 h to 80 h, preferentially from 40 h to 75 h, even more preferentially from 55 h to 75 h.
- T° c (t) (in °C) is the instantaneous temperature of the sheet which changes over time
- the calculation is performed over the time interval (in seconds) corresponding to the tempering processing time.
- the metallurgical state of the thin sheet after tempering is preferably a T8 state.
- thin sheets according to the invention or obtained according to the process of the invention is advantageous in fuselage structural elements or in aerospace applications such as the manufacture of rockets.
- composition D whose composition in % by weight is given in Table 1, was cast in the form of plates.
- Composition D corresponds to a composition according to the invention.
- Two plates were homogenized at 508° C. for 12 hours, then reheated before hot rolling at 505° C. for approximately 28 hours in order to obtain two thin sheets with respective thicknesses of 4.2 mm and 2.5 mm.
- the sheets then underwent solution treatment at 505°, stress relief by traction of 2% and tempering for 40 h at 155° C. (equivalent time of 63 h at 150° C.).
- the granular structure of the mid-thickness samples was characterized from the microscopic observation of metallographic sections in the L-TC direction after anodic oxidation under polarized light.
- the granular structure of the sheets is essentially recrystallized at mid-thickness.
- the samples were mechanically tested to determine their static mechanical properties (Table 3) as well as their toughness (Tables 4 and 5).
- the toughness characteristics were measured at full thickness and after facing of so as to have 1.2 mm specimens, the surfacing having been carried out on one side only; the specimens have a width of 760 mm.
- Table 5 discloses Aaeff_max for each of the cases.
- Aaeff_max represents the crack extension of the last point of the R-curve, valid according to ASTM E561-20. The last point is obtained either at the moment of the sudden rupture of the specimen, or possibly at the moment when the stress on the uncracked ligament exceeds on average the elastic limit of the material.
- the value of the tensile yield strength of the material R p o.2 is given in Table 4; it is measured after the R curve test, on an undeformed zone of the CT760 toughness specimen located above the initial crack.
- Alloys A, B, C, D were cast in the form of plates. Their composition in % by weight is indicated in Table 6. Alloys A, B, C have compositions outside the invention. They are representative of the disclosure of WO2016/051099.
- Ti targeted 0.03% by weight and Si, Fe targeted ⁇ 0.05% by weight.
- sheet D#1 reaches a yield strength R p 0.2 higher than the other sheets A#1, B#1, C#1. Its hardening kinetics is faster at the beginning of the tempering kinetics.
- Alloys A, E, F were cast in the form of plates. Their composition in % by weight is indicated in Table 9. Alloys A, E, F have compositions outside the invention. Alloy A is representative of the disclosure of WO2016/051099.
- Figure 3 shows that alloy D according to the invention has a better compromise R p o.2 - Aaeff_ max than alloys A, E and F.
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- Powder Metallurgy (AREA)
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Abstract
Description
Claims
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/730,122 US20250137102A1 (en) | 2022-01-28 | 2023-01-26 | Improved thin sheet made of aluminium-copper-lithium alloy |
| EP23706662.6A EP4469611A1 (fr) | 2022-01-28 | 2023-01-26 | Tole mince amelioree en alliage d'aluminium-cuivre-lithium |
| CN202380017755.XA CN118613598A (zh) | 2022-01-28 | 2023-01-26 | 由铝-铜-锂合金制成的改进薄板 |
| JP2024544637A JP2025504927A (ja) | 2022-01-28 | 2023-01-26 | アルミニウム-銅-リチウム合金製の改良された薄いシート |
| CA3246290A CA3246290A1 (fr) | 2022-01-28 | 2023-01-26 | Improved thin sheet made of aluminium-copper-lithium alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FRFR2200763 | 2022-01-28 | ||
| FR2200763A FR3132306B1 (fr) | 2022-01-28 | 2022-01-28 | Tôle mince améliorée en alliage d’aluminium-cuivre-lithium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023144492A1 true WO2023144492A1 (fr) | 2023-08-03 |
Family
ID=80999489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2023/050105 Ceased WO2023144492A1 (fr) | 2022-01-28 | 2023-01-26 | Tole mince amelioree en alliage d'aluminium-cuivre-lithium |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20250137102A1 (fr) |
| EP (1) | EP4469611A1 (fr) |
| JP (1) | JP2025504927A (fr) |
| CN (1) | CN118613598A (fr) |
| CA (1) | CA3246290A1 (fr) |
| FR (1) | FR3132306B1 (fr) |
| WO (1) | WO2023144492A1 (fr) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5455003A (en) | 1988-08-18 | 1995-10-03 | Martin Marietta Corporation | Al-Cu-Li alloys with improved cryogenic fracture toughness |
| FR2889542A1 (fr) * | 2005-08-05 | 2007-02-09 | Pechiney Rhenalu Sa | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| EP1891247A1 (fr) | 2005-06-06 | 2008-02-27 | Alcan Rhenalu | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| EP1966402A1 (fr) | 2005-12-20 | 2008-09-10 | Alcan Rhenalu | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| CN101967588A (zh) * | 2010-10-27 | 2011-02-09 | 中国航空工业集团公司北京航空材料研究院 | 一种耐损伤铝锂合金及其制备方法 |
| EP2766503A1 (fr) | 2011-10-14 | 2014-08-20 | Constellium France | Procédé de transformation amélioré de tôles en alliage al-cu-li |
| WO2016051099A1 (fr) | 2014-10-03 | 2016-04-07 | Constellium Issoire | Tôles isotropes en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion |
-
2022
- 2022-01-28 FR FR2200763A patent/FR3132306B1/fr active Active
-
2023
- 2023-01-26 EP EP23706662.6A patent/EP4469611A1/fr active Pending
- 2023-01-26 US US18/730,122 patent/US20250137102A1/en active Pending
- 2023-01-26 CA CA3246290A patent/CA3246290A1/fr active Pending
- 2023-01-26 WO PCT/FR2023/050105 patent/WO2023144492A1/fr not_active Ceased
- 2023-01-26 JP JP2024544637A patent/JP2025504927A/ja active Pending
- 2023-01-26 CN CN202380017755.XA patent/CN118613598A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5455003A (en) | 1988-08-18 | 1995-10-03 | Martin Marietta Corporation | Al-Cu-Li alloys with improved cryogenic fracture toughness |
| EP1891247A1 (fr) | 2005-06-06 | 2008-02-27 | Alcan Rhenalu | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| FR2889542A1 (fr) * | 2005-08-05 | 2007-02-09 | Pechiney Rhenalu Sa | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| EP1966402A1 (fr) | 2005-12-20 | 2008-09-10 | Alcan Rhenalu | Tole en aluminium-cuivre-lithium a haute tenacite pour fuselage d'avion |
| CN101967588A (zh) * | 2010-10-27 | 2011-02-09 | 中国航空工业集团公司北京航空材料研究院 | 一种耐损伤铝锂合金及其制备方法 |
| EP2766503A1 (fr) | 2011-10-14 | 2014-08-20 | Constellium France | Procédé de transformation amélioré de tôles en alliage al-cu-li |
| WO2016051099A1 (fr) | 2014-10-03 | 2016-04-07 | Constellium Issoire | Tôles isotropes en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion |
| US20170306454A1 (en) * | 2014-10-03 | 2017-10-26 | Constellium Issoire | Isotropic plates made from aluminum-copper-lithium alloy for manufacturing aircraft fuselages |
Also Published As
| Publication number | Publication date |
|---|---|
| FR3132306B1 (fr) | 2024-05-03 |
| JP2025504927A (ja) | 2025-02-19 |
| EP4469611A1 (fr) | 2024-12-04 |
| US20250137102A1 (en) | 2025-05-01 |
| CN118613598A (zh) | 2024-09-06 |
| CA3246290A1 (fr) | 2023-08-03 |
| FR3132306A1 (fr) | 2023-08-04 |
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