WO2019234326A1 - Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion - Google Patents
Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion Download PDFInfo
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- WO2019234326A1 WO2019234326A1 PCT/FR2019/051269 FR2019051269W WO2019234326A1 WO 2019234326 A1 WO2019234326 A1 WO 2019234326A1 FR 2019051269 W FR2019051269 W FR 2019051269W WO 2019234326 A1 WO2019234326 A1 WO 2019234326A1
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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
-
- 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 laminated products aluminum-copper-lithium alloys, more particularly, such products, their manufacturing processes and use, intended in particular for aeronautical and aerospace construction.
- Aluminum alloy rolled products are being developed to produce fuselage elements for the aerospace industry and the aerospace industry in particular.
- Aluminum - copper - lithium alloys are particularly promising for this type of product.
- U.S. Patent 5,032,359 discloses a broad family of aluminum-copper-lithium alloys in which the addition of magnesium and silver, particularly between 0.3 and 0.5 percent by weight, increases the mechanical strength. .
- US Pat. No. 5,455,003 describes a process for manufacturing Al-Cu-Li alloys which have improved mechanical strength and toughness at cryogenic temperature, in particular through appropriate work-hardening and tempering.
- Patent EP0584271 discloses an aluminum-based alloy useful in aeronautical and aerospace structures, having a low density, a high strength and a high fracture toughness, essentially corresponding to the formula CuaLibMgcAgdZreAlbal in which a, b, c, d, e and bal indicate the weight percentage of the alloying components, said percentages being 2.4 ⁇ a ⁇ 3.5, 1 , ⁇ B ⁇ 1, 8, 0.25 ⁇ c ⁇ 0.65, 0.25 ⁇ d ⁇ 0.65 and 0.08 ⁇ e ⁇ 0.25.
- US Pat. No. 7,438,772 describes alloys comprising, in percentage by weight, Cu: 3-5, Mg: 0.5-2, Li: 0.01-0.9 and discourages the use of higher lithium contents due to degradation of the compromise between toughness and mechanical strength.
- US Pat. No. 7,229,509 discloses an alloy comprising (% by weight): (2, 5-5, 5) Cu, (0.1 -2.5) Li, (0.2-1.0) Mg, (0, 2-0, 8) Ag, (0.2-0.8) Mn, 0.4 max Zr or other grain refining agents such as Cr, Ti, Hf, Se, V.
- US patent application 201 1/0247730 discloses alloys comprising (in% by weight), 2.75 to 5.0% Cu, 0.1 to 1.1% Li, 0.3 to 2.0% Ag, 0.2. at 0.8% Mg, 0.50 to 1.5% Zn, up to 1.0% Mn, with a Cu / Mg ratio of between 6.1 and 17, this alloy being insensitive to wrought.
- the patent application CN101967588 describes alloys of composition (in% by weight) Cu 2.8 - 4.0; Li 0.8 - 1.9; Mn 0.2-0.6; Zn 0.20-0.80, Zr 0.04-0.20, Mg 0.20-0.80, Ag 0.1-0.7, Si ⁇ 0.10, Fe ⁇ 0.10, Ti ⁇ 0.12.
- the patent FR3014448 describes a laminated and / or forged product whose thickness is between 14 and 100 mm, of aluminum alloy of composition, in% by weight, Cu: 1.8 - 2.6 Li: 1.3 1.8 Mg: 0.1 - 0.5 Mn: 0.1 - 0.5 and Zr ⁇ 0.05 or Mn ⁇ 0.05 and Zr 0.10 - 0.16 Ag: 0 - 0.5 Zn ⁇ 0 , Ti: 0.01 - 0.15 Fe: ⁇ 0.1 Si: ⁇ 0.1 Other elements ⁇ 0.05 each and ⁇ 0.15 in total, remains aluminum with a density of less than 2.670 g / cm3 characterized in that at mid-thickness the volume fraction of grains having a brass texture is between 25 and 40% and the texture index is between 12 and 18.
- the patent application US2009084474 describes a recrystallized aluminum alloy having a brass texture and a Goss texture, where the amount of brass texture exceeds the Goss texture amount and the recrystallized aluminum alloy has at least about the same yield strength and the same breaking strength as an uncrystallized alloy with the same product shape and similar thickness and quenching.
- EP 1 966 402 discloses an alloy comprising 2.1 to 2.8% by weight of Cu, 1.1 to 1.7% by weight of Li, 0.1 to 0.8% by weight of Ag. , 2 to 0.6% by weight of Mg, 0.2 to 0.6% by weight of Mn, an amount of Fe and Si of less than or equal to 0.1% by weight each, and unavoidable impurities at a rate of 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.
- the toughness be high in the T-L direction. Indeed, a large part of the fuselage is sized to withstand the internal pressure of the aircraft.
- the longitudinal direction of the sheets being generally positioned in the direction of the length of the aircraft, they are constrained in the transverse direction by the pressure. The cracks are then urged in the T-L direction. It may also be advantageous that the sheets have a low anisotropy of mechanical properties, especially between the directions L and TL.
- An object of the invention is a process for manufacturing a thin sheet of 0.5 to 8 mm thick aluminum alloy in which, successively
- said plate is homogenized at a temperature between 490 ° C and 535 ° C;
- said sheet is controlledly tensile with a permanent deformation of 0.5 to
- an income is made comprising heating at a temperature between 130 and 170 ° C and preferably between 150 and 160 ° C for 5 to 100 hours and preferably 10 to 40h.
- Another object of the invention is a sheet obtained by the method according to the invention, the mean grain size in the thickness measured by the method of intercepts on a L / TC cut in the direction L according to the ASTM El 12 standard. and expressed in pm is less than 66 t + 200 where t is the thickness of the sheet expressed in mm.
- Yet another object of the invention is the use of a thin sheet according to the invention in an aircraft fuselage panel.
- Figure 1 Metallographic section of the sheet A-1.
- Figure 2 Metallographic section of the C-2 sheet.
- Figure 3 Relationship between the elasticity limit in the direction TF and the stress intensity factor KR60 T-F measured on samples of width 760 mm for the sheets of Example 1.
- the static mechanical characteristics in tension in other words the tensile strength R m , the conventional yield stress at 0.2% elongation R P o, 2, and the elongation at break A%, are determined by a tensile test according to standard NF EN ISO 6892-1 (2016), the sampling and the direction of the test being defined by the standard EN 485-1 (2016).
- the mechanical characteristics are measured in full thickness.
- Line curve giving the effective stress intensity factor as a function of the effective crack extension is determined according to ASTM E 561.
- the critical stress intensity factor Kc in others the intensity factor which makes the crack unstable, is calculated from the curve R.
- the stress intensity factor Kco is also calculated by assigning the initial crack length at the beginning of the monotonic load, to the critical load . These two values are calculated for a specimen of the required form.
- K aPP represents the Kco factor corresponding to the specimen that was used to perform the R curve test.
- K ef r represents the Kc factor corresponding to the specimen that was used to perform the R curve test.
- Aa c n (max) represents the crack extension of the last point of the curve R, valid according to ASTM E561.
- the last point is obtained either at the time of the sudden rupture of the test piece, or possibly at the moment when the stress on the uncracked ligament exceeds on average the elastic limit of the material.
- the crack size at the end of the pre-fatigue cracking stage is W / 3 for M (T) type specimens, where W is the specimen width as defined in ASTM E561 (ASTM E561-10-2).
- the term "granular structure essentially recrystallized” is a granular structure such that the degree of recrystallization at 1 ⁇ 2 thickness is greater than 70% and preferably greater than 90%.
- the recrystallization rate is defined as the surface fraction on a metallographic section occupied by recrystallized grains.
- the present inventors have obtained sheets having a thickness of 0.5 to 8 mm presenting an advantageous compromise between the mechanical strength and the tenacity using the method according to the invention which notably comprises the combination of
- the thin sheets thus obtained have particularly advantageous properties, particularly as regards the tenacity in the T-L direction and the anisotropy of the mechanical properties.
- the copper content of the products according to the invention is between 2.3 and 2.7% by weight. In an advantageous embodiment of the invention, the copper content is at least
- the copper content is between 2.45 and 2.65% by weight and preferably between 2.50 and 2.60% by weight. In an advantageous embodiment of the invention the copper content is at most 2.65% by weight and preferably at most 2.60% by weight. In one embodiment of the invention, the copper content is at most 2.53% by weight.
- the copper content is too high, a very high toughness value in the TL direction may not be achieved.
- the copper content is too low, the minimum static mechanical characteristics are not reached.
- the lithium content of the products according to the invention is between 1, 3 and 1.6% by weight.
- the lithium content is between 1.35 and 1.55% by weight and preferably between 1.40% and 1.50% by weight.
- a minimum lithium content of 1.35% by weight and preferably 1.40% by weight is advantageous.
- a maximum lithium content of 1.55% by weight and preferably 1.50% by weight is advantageous, in particular to improve the compromise between toughness and mechanical strength.
- the addition of lithium can contribute to the increase of the mechanical strength and the toughness, a too high or too low content does not make it possible to obtain a very high value of toughness in the direction TL and / or a limit of sufficient elasticity.
- the addition of lithium makes it possible to reduce the density.
- the density of the products according to the invention is less than 2.65.
- the magnesium content of the products according to the invention is between 0.2 and 0.5% by weight and preferably between 0.25 and 0.45% by weight and preferably between 0.25 and 0.35% by weight. in weight.
- a minimum magnesium content of 0.25% by weight is advantageous.
- a maximum magnesium content of 0.45% by weight and preferably 0.40% by weight and preferably 0.35% by weight or even 0.30% by weight is advantageous.
- the manganese content is between 0.1 and 0.5% by weight, preferably between 0.2 and 0.4% by weight and preferably between 0.25 and 0.35% by weight.
- a minimum manganese content of 0.2% by weight and preferably 0.25% by weight is advantageous.
- a maximum manganese content of 0.4% by weight and preferably 0.35% by weight or even 0.33% by weight is advantageous.
- the titanium content is between 0.01 and 0.15% by weight.
- the iron and silicon contents are each at most 0.1% by weight.
- 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 zinc content is less than 0.3% by weight, preferably less than 0.2% by weight and preferably less than 0.1% by weight.
- the zinc content is advantageously less than 0.04% by weight.
- the unavoidable impurities are maintained at a content of less than or equal to 0.05% by weight each and 0.15% by weight in total.
- the method for manufacturing thin sheets according to the invention then comprises steps of casting, homogenization, hot rolling and optionally cold, dissolution, controlled pulling, quenching and tempering.
- the elaborated liquid metal bath is cast in a form of rolling plate.
- the rolling plate is then homogenized at a temperature between 490 ° C and 535 ° C.
- the homogenization time is between 5 and 60 hours.
- the homogenization temperature is at least 500 ° C. In one embodiment, the homogenization temperature is less than 515 ° C.
- the rolling plate After homogenization, the rolling plate is generally cooled to room temperature before being preheated to be hot deformed. Preheating aims to achieve a hot rolling entry temperature of between 400 and 445 ° C and preferably between 420 ° C and 440 ° C for deformation by hot rolling.
- the hot rolling is carried out so as to obtain a sheet typically of thickness 4 to 8 mm.
- the hot rolling exit temperature is less than 300 ° C and preferably less than 290 ° C.
- the specific conditions of hot rolling in combination with the composition according to the invention make it possible in particular to obtain a advantageous compromise between mechanical strength and toughness and low anisotropy of mechanical properties.
- the sheet obtained After hot rolling, it is optionally possible to cold roll the sheet obtained in particular to obtain a final thickness of between 0.5 and 3.9 mm.
- the final thickness is at most 7.0 mm and preferably at most 6.0 mm.
- the final thickness is at least 0.8 mm and preferably at least 1.2 mm.
- the sheet thus obtained is then dissolved between 450 and 515 ° C.
- the dissolution time is advantageously between 5 min to 8 h.
- the sheet thus dissolved is then quenched.
- the sheet then undergoes cold deformation by controlled traction with a permanent deformation of 0.5 to 6% and preferably 3 to 5%.
- Known steps such as rolling, planing, straightening and shaping may optionally be carried out after dissolution and quenching and before or after the controlled pull, however the total cold deformation after dissolution and quenching must remain inferior at 15% and preferably less than 10%.
- High cold deformation after dissolution and quenching cause the appearance of many shear bands passing through several grains, these shear bands being undesirable.
- no cold rolling is carried out after the dissolution.
- An income is achieved comprising heating at a temperature between 130 and 170 ° C and preferably between 140 and 160 ° C and preferably between 145 and 155 ° C for 5 to 100 hours and preferably 10 to 40h.
- the final metallurgical state is a T8 state.
- a short heat treatment is performed after controlled pulling and before tempering so as to improve the formability of the sheets.
- the sheets can thus be shaped by a process such as stretch-forming before being returned.
- the thin sheets obtained by the process according to the invention have a characteristic grain size.
- the average grain size in the thickness measured by the intercepts method on a L / TC cut in the L direction according to ASTM El 12 and expressed in ⁇ m is less than 66 t + 200 where t is the thickness the sheet metal expressed in mm, preferably less than 66 t + 150 and preferably less than 66 t + 100, for the thin sheets obtained by the process according to the invention.
- the granular structure of the sheets is advantageously essentially recrystallized.
- the thin sheets obtained by the process according to the invention have a toughness in the particularly advantageous TL direction.
- the sheets according to the invention also have a low anisotropy.
- the ratio between the yield strength difference between the directions L and TL and the yield strength in the direction L is less than 6% and preferably less than 5%.
- the resistance to intergranular corrosion of the sheets according to the invention is high.
- the sheet of the invention can be used without plating.
- thin sheets according to the invention in an aircraft fuselage panel is advantageous.
- the thin sheets according to the invention are also advantageous in aerospace applications such as the manufacture of rockets.
- the plates were converted according to the parameters indicated in Table 2.
- the transformation conditions used for alloy sheets A-1, A-2, B-1 and B-2 are in accordance with the invention.
- the income conditions have been defined to obtain a T8 state.
- the granular structure of the samples was characterized from microscopic observation of cross sections after anodic oxidation under polarized light on L / TC sections.
- the microstructures observed for samples A1 and C-2 are shown in Figures 1 and 2, respectively.
- the granular structure of the sheets was essentially recrystallized.
- the average grain sizes in the thickness measured by the intercepts method according to ASTM El 12 are shown in Table 3.
- Table 5 summarizes the results of the toughness tests for these samples.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112020023577-6A BR112020023577B1 (pt) | 2018-06-08 | 2019-05-29 | Folha fina, método para fabricá-la e uso da mesma |
US16/972,236 US20210363623A1 (en) | 2018-06-08 | 2019-05-29 | Thin sheets made of aluminium-copper-lithium alloy for aircraft fuselage manufacture |
CA3099351A CA3099351A1 (fr) | 2018-06-08 | 2019-05-29 | Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion |
EP19740635.8A EP3802897B1 (fr) | 2018-06-08 | 2019-05-29 | Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion |
CN201980036638.1A CN112236537A (zh) | 2018-06-08 | 2019-05-29 | 飞机机身制造用铝-铜-锂合金薄板 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR18/55005 | 2018-06-08 | ||
FR1855005A FR3082210B1 (fr) | 2018-06-08 | 2018-06-08 | Toles minces en alliage d’aluminium-cuivre-lithium pour la fabrication de fuselages d’avion |
Publications (1)
Publication Number | Publication Date |
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WO2019234326A1 true WO2019234326A1 (fr) | 2019-12-12 |
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Family Applications (1)
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PCT/FR2019/051269 WO2019234326A1 (fr) | 2018-06-08 | 2019-05-29 | Toles minces en alliage d'aluminium-cuivre-lithium pour la fabrication de fuselages d'avion |
Country Status (7)
Country | Link |
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US (1) | US20210363623A1 (fr) |
EP (1) | EP3802897B1 (fr) |
CN (1) | CN112236537A (fr) |
BR (1) | BR112020023577B1 (fr) |
CA (1) | CA3099351A1 (fr) |
FR (1) | FR3082210B1 (fr) |
WO (1) | WO2019234326A1 (fr) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5032359A (en) | 1987-08-10 | 1991-07-16 | Martin Marietta Corporation | Ultra high strength weldable aluminum-lithium alloys |
EP0584271A1 (fr) | 1991-05-14 | 1994-03-02 | Reynolds Metals Co | ALLIAGE DE Al-Li A RESISTANCE ELEVEE ET A FAIBLE DENSITE. |
US5455003A (en) | 1988-08-18 | 1995-10-03 | Martin Marietta Corporation | Al-Cu-Li alloys with improved cryogenic fracture toughness |
US7229509B2 (en) | 2003-05-28 | 2007-06-12 | Alcan Rolled Products Ravenswood, Llc | Al-Cu-Li-Mg-Ag-Mn-Zr alloy for use as structural members requiring high strength and high fracture toughness |
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 |
US7438772B2 (en) | 1998-06-24 | 2008-10-21 | Alcoa Inc. | Aluminum-copper-magnesium alloys having ancillary additions of lithium |
US20090084474A1 (en) | 2007-10-01 | 2009-04-02 | Alcoa Inc. | Recrystallized aluminum alloys with brass texture and methods of making the same |
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 |
US20110247730A1 (en) | 2010-04-12 | 2011-10-13 | Alcoa Inc. | 2xxx series aluminum lithium alloys having low strength differential |
FR3014448A1 (fr) | 2013-12-05 | 2015-06-12 | Constellium France | Produit en alliage aluminium-cuivre-lithium pour element d'intrados a proprietes ameliorees |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8771441B2 (en) | 2005-12-20 | 2014-07-08 | Bernard Bes | High fracture toughness aluminum-copper-lithium sheet or light-gauge plates suitable for fuselage panels |
EP2881478B1 (fr) * | 2012-08-01 | 2017-11-15 | UACJ Corporation | Feuille d'alliage d'aluminium et son procédé de fabrication |
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 |
-
2018
- 2018-06-08 FR FR1855005A patent/FR3082210B1/fr active Active
-
2019
- 2019-05-29 WO PCT/FR2019/051269 patent/WO2019234326A1/fr unknown
- 2019-05-29 CN CN201980036638.1A patent/CN112236537A/zh active Pending
- 2019-05-29 US US16/972,236 patent/US20210363623A1/en active Pending
- 2019-05-29 CA CA3099351A patent/CA3099351A1/fr active Pending
- 2019-05-29 BR BR112020023577-6A patent/BR112020023577B1/pt active IP Right Grant
- 2019-05-29 EP EP19740635.8A patent/EP3802897B1/fr active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5032359A (en) | 1987-08-10 | 1991-07-16 | Martin Marietta Corporation | Ultra high strength weldable aluminum-lithium alloys |
US5455003A (en) | 1988-08-18 | 1995-10-03 | Martin Marietta Corporation | Al-Cu-Li alloys with improved cryogenic fracture toughness |
EP0584271A1 (fr) | 1991-05-14 | 1994-03-02 | Reynolds Metals Co | ALLIAGE DE Al-Li A RESISTANCE ELEVEE ET A FAIBLE DENSITE. |
US7438772B2 (en) | 1998-06-24 | 2008-10-21 | Alcoa Inc. | Aluminum-copper-magnesium alloys having ancillary additions of lithium |
US7229509B2 (en) | 2003-05-28 | 2007-06-12 | Alcan Rolled Products Ravenswood, Llc | Al-Cu-Li-Mg-Ag-Mn-Zr alloy for use as structural members requiring high strength and high fracture toughness |
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 |
US20090084474A1 (en) | 2007-10-01 | 2009-04-02 | Alcoa Inc. | Recrystallized aluminum alloys with brass texture and methods of making the same |
US20110247730A1 (en) | 2010-04-12 | 2011-10-13 | Alcoa Inc. | 2xxx series aluminum lithium alloys having low strength differential |
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 |
FR3014448A1 (fr) | 2013-12-05 | 2015-06-12 | Constellium France | Produit en alliage aluminium-cuivre-lithium pour element d'intrados a proprietes ameliorees |
EP3077559A2 (fr) * | 2013-12-05 | 2016-10-12 | Constellium Issoire | Produit en alliage aluminium-cuivre-lithium pour élément d'intrados a propriétés améliorées |
Also Published As
Publication number | Publication date |
---|---|
EP3802897A1 (fr) | 2021-04-14 |
BR112020023577B1 (pt) | 2023-12-05 |
CN112236537A (zh) | 2021-01-15 |
FR3082210A1 (fr) | 2019-12-13 |
EP3802897B1 (fr) | 2022-11-16 |
CA3099351A1 (fr) | 2019-12-12 |
BR112020023577A2 (pt) | 2021-02-09 |
US20210363623A1 (en) | 2021-11-25 |
FR3082210B1 (fr) | 2020-06-05 |
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