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EP3610048B1 - Low-density aluminium-copper-lithium alloy products - Google Patents

Low-density aluminium-copper-lithium alloy products Download PDF

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EP3610048B1
EP3610048B1 EP18724942.0A EP18724942A EP3610048B1 EP 3610048 B1 EP3610048 B1 EP 3610048B1 EP 18724942 A EP18724942 A EP 18724942A EP 3610048 B1 EP3610048 B1 EP 3610048B1
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casting
weight
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French (fr)
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EP3610048A1 (en
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Juliette CHEVY
Philippe Jarry
Soizic BLAIS
Alireza Arbab
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Constellium Issoire SAS
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    • 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
    • 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
    • C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc

Definitions

  • the invention generally relates to wrought products made of aluminum-copper-lithium alloys, and more particularly to such products in the form of profiles intended to produce stiffeners in aeronautical construction.
  • Aluminum alloys containing lithium are very attractive 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.
  • their performance must reach that of commonly used alloys, particularly in terms of compromise between static mechanical strength properties (yield strength, breaking strength) and damage tolerance properties ( toughness, resistance to fatigue crack propagation), these properties being generally contradictory.
  • These alloys must also have sufficient corrosion resistance, be able to be shaped according to usual processes and have low residual stresses so that they can be fully machined.
  • the patent US 5,198,045 describes a family of Weldalite TM alloys comprising (in wt%) (2.4-3.5)Cu, (1.35-1.8)Li, (0.25-0.65)Mg, (0 .25-0.65)Ag, (0.08-0.25)Zr. Wrought products manufactured with these alloys combine a density of less than 2.64 g/cm 3 and an interesting compromise between mechanical resistance and toughness.
  • the patent US 7,229,509 describes a family of Weldalite TM alloys comprising (in wt%) (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, (up to 0.4) Zr or other elements such as Cr, Ti, Hf, Sc and V.
  • the examples shown have a compromise between mechanical resistance and toughness improved but their density is greater than 2.7 g/cm 3 .
  • the patent application WO2007/080267 describes a Weldalite TM alloy not containing zirconium intended for fuselage sheets comprising (in % by weight) (2.1-2.8) Cu, (1.1-1.7) Li, (0.2- 0.6) Mg, (0.1-0.8) Ag, (0.2-0.6) Mn.
  • alloy AA2196 comprising (in % by weight) (2.5-3.3) Cu, (1.4-2.1) Li, (0.25-0.8) Mg, (0 .25-0.6) Ag, (0.04-0.18) Zr and at most 0.35 Mn.
  • Yet another object of the invention is a process for manufacturing a wrought product comprising the casting of a raw form according to the process of the invention and steps of rolling or extrusion and/or forging, solution processing, quenching, stress relieving and optionally tempering.
  • Yet another object of the invention is a structural element incorporating at least one product obtained by the method of manufacturing a wrought product according to the invention or manufactured from an alloy product according to the invention.
  • alloys are expressed as a weight percentage based on the total weight of the alloy.
  • the designation of alloys is done in accordance with The Aluminum regulations. Association, known to those skilled in the art. Density depends on composition and is determined by calculation rather than a weight measurement method. Values are calculated in accordance with The Aluminum Association procedure, which is described on pages 2-12 and 2.13 of “Aluminum Standards and Data”. Definitions of metallurgical conditions are given in European standard EN 515 (2009).
  • the static mechanical characteristics in other words the breaking strength R m , the conventional yield strength at 0.2% elongation R p0.2 (“yield strength”) and l elongation at break A, are determined by a tensile test according to standard EN 10002-1 (2001), the sampling and direction of the test being defined by standard EN 485-1 (2016).
  • the stress intensity factor (K Q ) is determined according to ASTM E 399 (2012).
  • the ASTM E 399 (2012) standard gives paragraphs 9.1.3 and 9.1.4 criteria which allow us to determine whether K Q is a valid value of K 1C .
  • a K 1C value is always a K Q value, the converse not being true.
  • the criteria of paragraphs 9.1.3 and 9.1.4 of standard ASTM E399 (2012) are not always verified, however for a given specimen geometry, the values of K Q presented are always comparable to each other, the specimen geometry making it possible to obtain a valid value of K 1C not always being accessible given the constraints linked to the dimensions of the sheets or profiles.
  • the thickness of the profiles is defined according to standard EN 2066:2001: the cross section is divided into elementary rectangles of dimensions A and B; A always being the largest dimension of the elementary rectangle and B can be considered as the thickness of the elementary rectangle.
  • structural element or “structural element” of a mechanical construction a mechanical part for which the static and/or dynamic mechanical properties are particularly important for the performance of the structure, and for which a structural calculation is usually prescribed or carried out.
  • these structural elements include in particular the elements which make up the fuselage (such as the fuselage skin), the fuselage stiffeners or stringers (stringers), the bulkheads (bulkheads), the fuselage frames.
  • fuselage (circumferential frames), the wings (such as the wing skin), the stiffeners (stringers or stiffeners), the ribs (ribs) and spars (spars)) and the empennage composed in particular of horizontal and vertical stabilizers (horizontal or vertical stabilizers), as well as floor beams, seat tracks and doors.
  • the present inventors have found that, surprisingly, for certain AlCuLiMgMnZr alloys of particularly low density containing less than 0.1% by weight of silver and a joint addition of copper, lithium, magnesium and manganese, the specific choice of a particular zirconium content, depending on the lithium content, makes it possible to very significantly improve the robustness of the manufacturing process while maintaining for the product a satisfactory compromise between mechanical resistance and tolerance to damage.
  • robustness of the manufacturing process we mean here generating little scrap linked in particular to hot slot problems and allowing the use of a significant quantity of recycled alloy.
  • the copper content of the alloy according to the invention for which both the compromise of properties and the improvement of the feasibility of the process are obtained is 2.4 to 3.2% by weight.
  • the copper content is 2.5 to 3.0% by weight and preferably 2.6 to 2.9% by weight.
  • the copper content is 2.4 to 2.6% by weight.
  • the lithium content of the alloy according to the invention is such that it makes it possible to obtain a product having a particularly interesting density, in particular a density less than 2.63 g/cm 3 , more particularly less than 2.62 g /cm 3 and, more particularly, less than or equal to 2.61 g/cm 3 .
  • the lithium content of the alloy is thus greater than 1.6% by weight, preferably greater than 1.7% by weight and, even more preferably, greater than 1.9% by weight.
  • Such a lithium content induces a very high sensitivity to oxidation, hydrogenation and hot cracking, causing difficulties in casting the alloy and, consequently, requires very specific manufacturing processes.
  • Requirement WO2015/086921 describes in particular the fact that, lithium being particularly oxidizable, the casting of aluminum-copper-lithium alloys generates more fatigue crack initiation sites than for type 2XXX alloys without lithium.
  • problems of hot splitting or cracking in the core of the raw form during casting are also generally observed.
  • the problem of hot cracking can be remedied by strongly refining the alloy during casting. It is in fact known that the risk of hot cracking is higher as the casting grain is coarser. A reduction in grain size as well as a change in grain shape can be achieved by adding large amounts of grain refiner during casting. Typical grain refiners are Al3%Ti0.15%C, Al1%Ti0.15%C, Al3%Ti1%B and Al5%Ti1%B in wire form usually added in-line. The addition of these agents induces the dispersion of fine boride or carbide particles in the liquid metal which will serve as grain nucleation sites during solidification.
  • grain refining agents comprising titanium as well as that of remelting of alloys also containing titanium rapidly induces, as the alloy production cycles progress, an increase in the content of total titanium of the alloy, which degrades the damage tolerance properties of the wrought product and thus limits the possible contribution of recycled metal in the load.
  • an AlCuLiMgMnZr alloy according to the invention having in particular particular Li and Zr contents, made it possible to improve the robustness of the manufacturing process and to limit or even to eliminate the supply of grain refining agents.
  • the lithium content of the alloy according to the invention is thus greater than 1.6% by weight, preferably greater than 1.7% by weight and, even more preferably, greater than 1.9% by weight.
  • the Li content of the alloy is 1.7 to 2.3% by weight or another 2.0 to 2.2% by weight.
  • the high lithium content in particular exacerbates the sensitivity to oxidation of the liquid metal bath and promotes core cracking problems during casting, which requires reducing the casting speed.
  • the zirconium content is 0.13 to 0.16% by weight; and more preferably from 0.14 to 0.15% by weight.
  • the present inventors believe that the alloy composition according to the precisely selected invention allows the formation of cubic crystalline phases Al 3 Zr and Al 3 (Zr, Li) which are structurally similar to the phase metastable Al 3 Li which is known to precipitate by demixing of the solid solution during tempering after solution and quenching but which is not supposed to form from the liquid, the known stable form being the tetragonal variety.
  • the formation of such phases thanks to the specifically selected composition of the alloy could be the origin of grain nucleation sites during the solidification of the as-cast form, thus allowing the formation of an extremely fine granular structure in the presence of a conventional quantity of grain refining agent or making it possible to limit, possibly eliminate, the supply of grain refining agent during casting.
  • the zirconium content of the alloy according to the invention is advantageously such that Zr ⁇ -0.06*Li + 0.242, preferably such that Zr ⁇ -0.06*Li + 0.2575.
  • the Li and Zr contents of the alloy according to the invention are such that Zr*Li ⁇ 0.235, preferably Zr*Li ⁇ 0.242, more preferably Zr*Li ⁇ 0.275.
  • the magnesium content is 0.3 to 0.9% by weight and, preferably, 0.5 to 0.7% by weight.
  • the manganese content is 0.2 to 0.6% by weight, preferably 0.3 to 0.6% by weight and, even more preferably 0.4 to 0.5% by weight. Manganese in particular makes it possible to achieve a satisfactory compromise of properties for the wrought product.
  • the silver content is less than 0.15% by weight, preferably less than 0.1% by weight and, more preferably still less than 0.05% by weight.
  • the present inventors have found that the advantageous compromise between mechanical strength and damage tolerance known for alloys typically containing about 0.3% by weight of silver can be obtained for alloys containing essentially no silver with the selection composition carried out.
  • the zinc content is less than 1.0% by weight, preferably less than 0.9% by weight. According to a first particular embodiment, the zinc content is between 0.1 and 0.5% by weight and preferably between 0.2 and 0.4% by weight. According to a second particular embodiment, the zinc content is less than 0.05% by weight.
  • the alloy also contains at least one element capable of contributing to grain size control selected from Ti, Cr, Sc, Hf and V, the amount of the element, if chosen, being 0.01 to 0 .15% by weight, preferably 0.01 to 0.05% for Ti, from 0.01 to 0.15% by weight, preferably 0.02 to 0.1% by weight for Sc, from 0.01 to 0 .3% by weight and preferably from 0.02 to 0.1% by weight for Cr and V and from 0.01 to 0.5% by weight for Hf.
  • titanium is chosen in the aforementioned contents and even more advantageously in a content ranging from 0.01 to 0.03% by weight.
  • the unavoidable impurities include iron and silicon, these impurities have a total content of less than 0.20% by weight and preferably respectively a content of less than 0.08% by weight and 0.06% by weight for iron and silicon.
  • silicon; the other elements are impurities which preferably have a content of less than 0.05% by weight each and 0.15% by weight in total.
  • the process for manufacturing raw casting products according to the invention comprises stages of preparation, casting and solidification of the raw form. These steps are followed, for the production of the wrought products according to the invention, by the steps of rolling or extrusion and/or forging, solution processing, quenching, stress relief and optionally tempering.
  • the grain size of the AlCuLiMgMnZr alloy according to the invention in the as-cast state, obtained by one of the processes according to the invention is less than 110 ⁇ m, preferably less than or equal to 105 ⁇ m and , more preferably even less than 100 ⁇ m for raw casting shapes with a thickness or diameter greater than 150 mm, preferably greater than 250 mm and even more preferably greater than 300 mm.
  • the grain size of the AlCuLiMgMnZr alloy according to the invention in the as-cast state, obtained by one of the processes according to the invention is less than or equal to 95 ⁇ m, preferably less than 90 ⁇ m for as-cast forms with a thickness or diameter greater than 150 mm, preferably greater than 250 mm and even more preferably greater than 300 mm.
  • an object of the invention is a structural element incorporating at least one product according to the invention or a product manufactured using a process according to the invention.
  • a structural element incorporating at least one product according to the invention or manufactured from such a product is advantageous, in particular for aeronautical construction.
  • the products according to the invention are particularly advantageous for the production of structural elements such as fuselage or wing stiffeners, floor beams and seat rails.
  • Table 1 Composition in % by weight and density of AlCuLiMgMnZr alloys Alloy Cu Li Mg Zn Ag Mn Zr Ti Density (g/cm 3 ) AA2196 2.5-3.3 1.4-2.1 0.25-0.8 ⁇ 0.35 0.25-0.6 ⁇ 0.35 0.04-0.18 ⁇ 0.1 2.63 68 3.00 1.67 0.35 0.52 0.02 0.06 0.143 0.040 2.63 69 3.00 1.66 0.33 0.52 0.05 0.31 0.144 0.041 2.63 70 2.55 1.78 0.62 0.52 0.02 0.32 0.146 0.040 2.62 71 2.56 2.00 0.61 0.51 0.02 0.33 0.147 0.038 2.60 72 2.45 1.91 0.63 0.82 0.06 0.32 0.145 0.038 2.61 73 2.52 2.16 0.59 0.60 0.01 0.08 0.124 0.041 2.59 76 2.49 1.93 0.57 0.049 0.03 0.32 0.140 0.038 2.60 Fe + Si ⁇ 0.2% by weight, other elements ⁇ 0.05% by weight each and
  • AA2196 alloy billets (alloys 2 and 5) whose composition is given in Table 3 below, were homogenized for 8 hours at 500 °C then 24 hours at 527 °C (alloy 2) or 8 hours at 520 °C (alloy 5). Billets of alloy 76 from Example 1 were homogenized for 10 hours at 534°C.
  • the billets were then reheated to 450 °C +/- 40 °C then hot-spun to obtain W profiles according to the Figure 3 for alloy 2 and Z according to Figure 4 for alloys 5 and 76.
  • the profiles thus obtained were put in solution at 524 °C, quenched and tensile with a permanent elongation of between 2 and 5%. Tempering was carried out for 48 hours at 152°C.
  • Table 3 Composition in % by weight and density of AA2196 alloy Alloy If Fe Cu Mn Mg Zn Ti Zr Li Ag Density (g/cm 3 ) 2 0.04 0.05 2.83 0.33 0.36 0.02 0.02 0.11 1.59 0.38 2.64 5 0.03 0.04 2.90 0.31 0.40 0.01 0.03 0.1 1.67 0.38 2.64 Other elements ⁇ 0.05% by weight each and ⁇ 0.15% in total
  • Samples taken at the end of the profile were tested to determine their static mechanical properties as well as their toughness (K q ).
  • the location of the samples is indicated in dotted lines on the figures 3 And 4 .
  • the test pieces used for measuring the static properties were 10 mm in diameter and taken in such a way that the direction of the axis of the test piece corresponds to the spinning direction (direction L).
  • Table 4 Yield strength Rp0.2 (L) in MPa and toughness Kq (LT) in MPaVm Alloy Rp0.2(L) Kq (LT) 2 522 37.6 5 536 38.2 76 512 43.4
  • the composition of the liquid metal is that of the solidified alloys, the subsequent solidification being carried out without the conventional addition of refining agent so as to highlight the contribution intrinsic to the composition of the alloy to the law of germination.
  • the grain sizes obtained are different from those obtained in vertical casting in the presence of refining agent, but the possibility of self-inoculation of the alloy in a certain composition range can be demonstrated by this test which thus makes it possible to specify the position of the boundary of the domain of interest in the Zr vs Li plane.
  • the cooling rate is 3.5K.s -1 .
  • the pawn which has the shape of a section of cone 65mm high and whose circular bases have respective radii of 25mm and 65mm, is demolded and cut along its axis.
  • the grain measurement is carried out 38 mm from the small face.
  • the upper part of the pawn thus cut out was polished then underwent anodic oxidation before being observed under polarized light.
  • the grain size was measured on this upper part thus prepared by an intercept method according to the ASTM El12 standard.
  • Table 5 Composition in % by weight and density of the AlCuLiMgMnZr alloy used Alloy If Fe Cu Mn Mg Ti Li Zr Grain size (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) ( ⁇ m) 1 0.02 0.037 3.22 0.31 0.37 0.03 1.80 0.101 823 2 0.02 0.039 3.25 0.31 0.36 0.03 1.91 0.101 1017 3 0.02 0.039 3.31 0.31 0.38 0.03 2.07 0.101 913 4 0.02 0.038 3.26 0.31 0.37 0.03 1.83 0.115 927 5 0.02 0.038 3.25 0.31 0.37 0.03 1.93 0.120 799 6 0.02 0.039 3.31 0.31 0.36 0.03 2.07 0.116 698 8 0.02 0.040 3.3 0.31 0.50 0.03 2.08 0.122 490 10 0.02 0.039 3.21 0.31 0.33 0.03 1.79

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Description

Domaine de l'inventionField of the invention

L'invention concerne en général les produits corroyés en alliages aluminium-cuivre-lithium, et plus particulièrement de tels produits sous la forme de profilés destinés à réaliser des raidisseurs en construction aéronautique.The invention generally relates to wrought products made of aluminum-copper-lithium alloys, and more particularly to such products in the form of profiles intended to produce stiffeners in aeronautical construction.

Etat de la techniqueState of the art

Un effort de recherche continu est réalisé afin de développer des matériaux qui puissent simultanément réduire le poids et augmenter l'efficacité des structures d'avions à hautes performances. Les alliages d'aluminium contenant du lithium sont très intéressants à cet égard, car le lithium peut réduire la densité de l'aluminium de 3 % et augmenter le module d'élasticité de 6 % pour chaque pourcent en poids de lithium ajouté. Pour que ces alliages soient sélectionnés dans les avions, leur performance doit atteindre celle des alliages couramment utilisés, en particulier en terme de compromis entre les propriétés de résistance mécanique statique (limite élastique, résistance à la rupture) et les propriétés de tolérance aux dommages (ténacité, résistance à la propagation des fissures en fatigue), ces propriétés étant en général antinomiques. Ces alliages doivent de plus présenter une résistance à la corrosion suffisante, pouvoir être mis en forme selon les procédés habituels et présenter de faibles contraintes résiduelles de façon à pouvoir être usinés de façon intégrale.A continuous research effort is being carried out to develop materials that can simultaneously reduce the weight and increase the efficiency of high-performance aircraft structures. Aluminum alloys containing lithium are very attractive 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. For these alloys to be selected in aircraft, their performance must reach that of commonly used alloys, particularly in terms of compromise between static mechanical strength properties (yield strength, breaking strength) and damage tolerance properties ( toughness, resistance to fatigue crack propagation), these properties being generally contradictory. These alloys must also have sufficient corrosion resistance, be able to be shaped according to usual processes and have low residual stresses so that they can be fully machined.

On connait plusieurs alliages Al-Cu-Li pour lesquels une addition d'argent est effectuée.Several Al-Cu-Li alloys are known for which an addition of silver is carried out.

Le brevet US 5,032,359 décrit une vaste famille d'alliages aluminium-cuivre-lithium dans lesquels l'addition de magnésium et d'argent, en particulier entre 0,3 et 0,5 pourcent en poids, permet d'augmenter la résistance mécanique. Ces alliages sont souvent connus sous le nom commercial « Weldalite ™ ».The patent US 5,032,359 describes a large family of aluminum-copper-lithium alloys in which the addition of magnesium and silver, in particular between 0.3 and 0.5 percent by weight, makes it possible to increase the mechanical strength. These alloys are often known by the trade name “Weldalite ™ ”.

Le brevet US 5,198,045 décrit une famille d'alliages Weldalite ™ comprenant (en % en poids) (2,4-3,5)Cu, (1,35-1,8)Li, (0,25-0,65)Mg, (0,25-0,65)Ag, (0,08-0,25) Zr. Les produits corroyés fabriqués avec ces alliages combinent une densité inférieure à 2,64 g/cm3 et un compromis entre la résistance mécanique et la ténacité intéressant.The patent US 5,198,045 describes a family of Weldalite ™ alloys comprising (in wt%) (2.4-3.5)Cu, (1.35-1.8)Li, (0.25-0.65)Mg, (0 .25-0.65)Ag, (0.08-0.25)Zr. Wrought products manufactured with these alloys combine a density of less than 2.64 g/cm 3 and an interesting compromise between mechanical resistance and toughness.

Le brevet US 7,229,509 décrit une famille d'alliages Weldalite ™ comprenant (en % en poids) (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, (jusque 0,4) Zr ou d'autres éléments tels que Cr, Ti, Hf, Sc et V. Les exemples présentés ont un compromis entre la résistance mécanique et la ténacité amélioré mais leur densité est supérieure à 2,7 g/cm3.The patent US 7,229,509 describes a family of Weldalite ™ alloys comprising (in wt%) (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, (up to 0.4) Zr or other elements such as Cr, Ti, Hf, Sc and V. The examples shown have a compromise between mechanical resistance and toughness improved but their density is greater than 2.7 g/cm 3 .

La demande de brevet WO2007/080267 décrit un alliage Weldalite ™ ne contenant pas de zirconium destiné à des tôles de fuselage comprenant (en % en poids) (2,1-2,8) Cu, (1,1-1,7) Li, (0,2-0,6) Mg, (0,1-0,8) Ag, (0,2-0,6) Mn.The patent application WO2007/080267 describes a Weldalite ™ alloy not containing zirconium intended for fuselage sheets comprising (in % by weight) (2.1-2.8) Cu, (1.1-1.7) Li, (0.2- 0.6) Mg, (0.1-0.8) Ag, (0.2-0.6) Mn.

On connait par ailleurs l'alliage AA2196 comprenant (en % en poids) (2,5-3,3)Cu, (1,4-2,1) Li, (0,25-0,8) Mg, (0,25-0,6) Ag, (0,04-0,18) Zr et au plus 0,35 Mn.We also know the alloy AA2196 comprising (in % by weight) (2.5-3.3) Cu, (1.4-2.1) Li, (0.25-0.8) Mg, (0 .25-0.6) Ag, (0.04-0.18) Zr and at most 0.35 Mn.

La limitation de la quantité d'argent est économiquement très favorable. Cependant, on constate que les produits selon l'art antérieur faits en alliage ne contenant essentiellement pas d'argent, par exemple AA2099, ne permettent pas d'obtenir des propriétés aussi avantageuses que celles des produits faits avec des alliages contenant de l'argent tels que l'alliage AA2196. Notamment le compromis avantageux entre la résistance mécanique et la ténacité n'est pas atteint, tout en maintenant une résistance à la corrosion satisfaisante.Limiting the amount of money is economically very favorable. However, we note that the products according to the prior art made from an alloy containing essentially no silver, for example AA2099, do not make it possible to obtain properties as advantageous as those of products made with alloys containing silver. such as alloy AA2196. In particular, the advantageous compromise between mechanical strength and toughness is not achieved, while maintaining satisfactory corrosion resistance.

Il existe un besoin pour des produits en alliage aluminium-cuivre-lithium présentant une densité particulièrement réduite et des propriétés améliorées par rapport à celles des produits connus ne contenant essentiellement pas d'argent, en particulier en termes de compromis entre les propriétés de résistance mécanique statique et les propriétés de tolérance aux dommages, de résistance à la corrosion. Ces produits en alliage aluminium-cuivre-lithium doivent en outre pouvoir être fabriqués à l'aide de procédés robustes et économiquement avantageux, c'est-à-dire générant peu de rebuts liés en particulier à des problèmes de fentes à chaud et permettant l'utilisation d'une quantité importante d'alliage recyclé.There is a need for aluminum-copper-lithium alloy products having particularly reduced density and improved properties compared to those of known products containing essentially no silver, particularly in terms of compromise between mechanical strength properties. static and damage tolerance, corrosion resistance properties. These aluminum-copper-lithium alloy products must also be able to be manufactured using robust and economical processes. advantageous, that is to say generating little scrap linked in particular to hot slot problems and allowing the use of a significant quantity of recycled alloy.

Objet de l'inventionObject of the invention

Un premier objet de l'invention est un produit en alliage à base d'aluminium comprenant, en % en poids,

  • Cu : 2,4-3,2 ; préférentiellement 2,5-3,0 ;
  • Li : 1,6-2,3 ; préférentiellement 1,7-2,2 ;
  • Mg : 0,3-0,9 ; préférentiellement 0,5-0,7 ;
  • Mn : 0,2 - 0,6 ; préférentiellement 0,3-0,6 ;
  • Zr : 0,13-0,16 ; préférentiellement 0,13-0,15 ; et
    tel que Zr ≥ -0,06*Li + 0,242 ;
  • Zn : < 1,0 préférentiellement <0,9 ;
  • Ag : < 0,15 ; préférentiellement <0,1 ;
  • Fe + Si ≤ 0,20 ;
  • optionnellement au moins un élément parmi Ti, Sc, Cr, Hf et V, la teneur de l'élément s'il est choisi, étant :
    • Ti : 0,01 - 0,15 ; préférentiellement 0,01-0,05 ;
    • Sc : 0,01 - 0,15, préférentiellement 0,02-0,1 ;
    • Cr : 0,01 - 0,3, préférentiellement 0,02-0,1 ;
    • Hf: 0,01 - 0, 5 ;
    • V : 0,01 - 0,3, préférentiellement 0,02-0,1 ;
  • autres éléments ≤ 0,05 chacun et ≤ 0,15 au total, reste aluminium.
A first object of the invention is an aluminum-based alloy product comprising, in % by weight,
  • Cu: 2.4-3.2; preferably 2.5-3.0;
  • Li: 1.6-2.3; preferably 1.7-2.2;
  • Mg: 0.3-0.9; preferably 0.5-0.7;
  • Mn: 0.2 - 0.6; preferably 0.3-0.6;
  • Zr: 0.13-0.16; preferably 0.13-0.15; And
    such that Zr ≥ -0.06*Li + 0.242;
  • Zn: <1.0 preferably <0.9;
  • Ag: <0.15; preferably <0.1;
  • Fe + Si ≤ 0.20;
  • optionally at least one element from Ti, Sc, Cr, Hf and V, the content of the element if chosen, being:
    • Ti: 0.01 - 0.15; preferably 0.01-0.05;
    • Sc: 0.01 - 0.15, preferably 0.02-0.1;
    • Cr: 0.01 - 0.3, preferably 0.02-0.1;
    • Hf: 0.01 - 0.5;
    • V: 0.01 - 0.3, preferably 0.02-0.1;
  • other elements ≤ 0.05 each and ≤ 0.15 in total, remains aluminum.

Un second objet l'invention est un produit en alliage à base d'aluminium comprenant, en % en poids,

  • Cu : 2,4-3,2 ; préférentiellement 2,5-3,0 ;
  • Li : 1,6-2,3 ; préférentiellement 1,7-2,2 ;
  • Mg : 0,3-0,9 ; préférentiellement 0,5-0,7 ;
  • Mn : 0,2 - 0,6 ; préférentiellement 0,3-0,6 ;
  • Zr : 0,13-0,16 ; préférentiellement 0,13-0,15 ; et
    tel que Zr*Li ≥ 0,235, préférentiellement Zr*Li ≥ 0,275;
  • Zn : < 1,0 préférentiellement <0,9 ;
  • Ag : < 0,15 ; préférentiellement <0,1 ;
  • Fe + Si ≤ 0,20 ;
  • optionnellement au moins un élément parmi Ti, Sc, Cr, Hf et V, la teneur de l'élément s'il est choisi, étant :
    • Ti : 0,01 - 0,15 ; préférentiellement 0,01-0,05 ;
    • Sc : 0,01 - 0,15, préférentiellement 0,02-0,1 ;
    • Cr : 0,01 - 0,3, préférentiellement 0,02-0,1 ;
    • Hf: 0,01 - 0, 5 ;
    • V : 0,01 - 0,3, préférentiellement 0,02-0,1 ;
  • autres éléments ≤ 0,05 chacun et ≤ 0,15 au total, reste aluminium.
A second object of the invention is an aluminum-based alloy product comprising, in % by weight,
  • Cu: 2.4-3.2; preferably 2.5-3.0;
  • Li: 1.6-2.3; preferably 1.7-2.2;
  • Mg: 0.3-0.9; preferably 0.5-0.7;
  • Mn: 0.2 - 0.6; preferably 0.3-0.6;
  • Zr: 0.13-0.16; preferably 0.13-0.15; And
    such that Zr*Li ≥ 0.235, preferably Zr*Li ≥ 0.275;
  • Zn: <1.0 preferably <0.9;
  • Ag: <0.15; preferably <0.1;
  • Fe + Si ≤ 0.20;
  • optionally at least one element from Ti, Sc, Cr, Hf and V, the content of the element if chosen, being:
    • Ti: 0.01 - 0.15; preferably 0.01-0.05;
    • Sc: 0.01 - 0.15, preferably 0.02-0.1;
    • Cr: 0.01 - 0.3, preferably 0.02-0.1;
    • Hf: 0.01 - 0.5;
    • V: 0.01 - 0.3, preferably 0.02-0.1;
  • other elements ≤ 0.05 each and ≤ 0.15 in total, remains aluminum.

Un autre objet de l'invention est un procédé de fabrication d'un produit brut de coulée en alliage d'aluminium selon l'invention comprenant les étapes :

  1. a) élaboration d'un bain de métal liquide ;
  2. b) coulée d'une forme brute à partir dudit bain de métal liquide ;
  3. c) solidification de la forme brute en une billette, une plaque de laminage ou une ébauche de forge ;
  • caractérisé en ce que la coulée est réalisée sans ajout d'affinant du grain ou en ajoutant un affinant comprenant (i) Ti et (ii) B ou C et tel que la teneur en B provenant de l'agent affinant est inférieure à 20 ppm, préférentiellement inférieure à 10 ppm et, plus préférentiellement encore, inférieure à 5 ppm et celle de C inférieure à 3 ppm, préférentiellement inférieure à 2 ppm et, plus préférentiellement encore, inférieure à 1 ppm et /ou
  • caractérisé en ce que la coulée est réalisée, pour une forme brute de coulée d'épaisseur E (mm) ou de diamètre D (mm) supérieur à 150 mm à une vitesse de coulée v (en mm/min) supérieure à :
    • 30 à 40 pour une forme brute de coulée type plaque,
    • (9000 à 12000)/D pour une forme brute de coulée type billette.
Another object of the invention is a process for manufacturing a raw aluminum alloy casting product according to the invention comprising the steps:
  1. a) development of a liquid metal bath;
  2. b) casting a raw form from said bath of liquid metal;
  3. c) solidifying the raw form into a billet, rolling plate or forging blank;
  • characterized in that the casting is carried out without adding a grain refiner or by adding a refiner comprising (i) Ti and (ii) B or C and such that the B content coming from the refiner is less than 20 ppm , preferably less than 10 ppm and, even more preferably, less than 5 ppm and that of C less than 3 ppm, preferably less than 2 ppm and, even more preferably, less than 1 ppm and/or
  • characterized in that the casting is carried out, for a raw casting form of thickness E (mm) or diameter D (mm) greater than 150 mm at a casting speed v (in mm/min) greater than:
    • 30 to 40 for a raw plate type casting form,
    • (9000 to 12000)/D for a raw billet type casting form.

Encore un autre objet de l'invention est un procédé de fabrication d'un produit corroyé comprenant la coulée d'une forme brute selon le procédé de l'invention et des étapes de laminage ou extrusion et/ou forgeage, mise en solution, trempe, détensionnement et optionnellement revenu.Yet another object of the invention is a process for manufacturing a wrought product comprising the casting of a raw form according to the process of the invention and steps of rolling or extrusion and/or forging, solution processing, quenching, stress relieving and optionally tempering.

Encore un autre objet de l'invention est un élément de structure incorporant au moins un produit obtenu par le procédé de fabrication de produit corroyé selon l'invention ou fabriqué à partir d'un produit en alliage selon l'invention.Yet another object of the invention is a structural element incorporating at least one product obtained by the method of manufacturing a wrought product according to the invention or manufactured from an alloy product according to the invention.

Description des figuresDescription of figures

  • La figure 1 représente la taille des grains de coulée (µm) des alliages AlCuLiMgMnZr de l'exemple 1 placée dans le diagramme Zr (% en poids) en fonction de Li (% en poids). Les équations Zr = -0.06Li + 0.2575 et Zr = -0.06Li + 0.242 sont représentées.There figure 1 represents the size of the casting grains (µm) of the AlCuLiMgMnZr alloys of Example 1 placed in the diagram Zr (% by weight) as a function of Li (% by weight). The equations Zr = -0.06Li + 0.2575 and Zr = -0.06Li + 0.242 are shown.
  • La figure 2 représente la taille des grains de coulée (µm) des alliages AlCuLiMgMnZr de l'exemple 1 placée dans le diagramme Zr (% en poids) en fonction de Li (% en poids). Les équations Zr = 0.275/Li et Zr = 0.235/Li sont représentées.There figure 2 represents the size of the casting grains (µm) of the AlCuLiMgMnZr alloys of Example 1 placed in the diagram Zr (% by weight) as a function of Li (% by weight). The equations Zr = 0.275/Li and Zr = 0.235/Li are shown.
  • La figure 3 représente la forme des profilés W de l'exemple 2 (on entend par « forme » la section transversale dudit profilé).There Figure 3 represents the shape of the W profiles of Example 2 (the term “shape” means the cross section of said profile).
  • La figure 4 représente la forme des profilés Z de l'exemple 2 (on entend par « forme » la section transversale dudit profilé).There figure 4 represents the shape of the Z profiles of Example 2 (the term “shape” means the cross section of said profile).
  • La figure 5 représente la taille des grains de coulée (µm) des alliages AlCuLiMgMnZr de l'exemple 3 placée dans le diagramme Zr (% en poids) en fonction de Li (% en poids). Les équations Zr = -0.06Li + 0.2575 et Zr = -0.06Li + 0.242 sont représentées.There Figure 5 represents the size of the casting grains (µm) of the AlCuLiMgMnZr alloys of Example 3 placed in the diagram Zr (% by weight) as a function of Li (% by weight). The equations Zr = -0.06Li + 0.2575 and Zr = -0.06Li + 0.242 are shown.
  • La figure 6 représente la taille des grains de coulée (µm) des alliages AlCuLiMgMnZr de l'exemple 3 placée dans le diagramme Zr (% en poids) en fonction de Li (% en poids). Les équations Zr = 0.275/Li et Zr = 0.235/Li sont représentées.There Figure 6 represents the size of the casting grains (µm) of the AlCuLiMgMnZr alloys of Example 3 placed in the diagram Zr (% by weight) as a function of Li (% by weight). The equations Zr = 0.275/Li and Zr = 0.235/Li are shown.
Description de l'inventionDescription of the invention

Sauf mention contraire, toutes les indications concernant la composition chimique des alliages sont exprimées comme un pourcentage en poids basé sur le poids total de l'alliage. La désignation des alliages se fait en conformité avec les règlements de The Aluminium Association, connus de l'homme du métier. La densité dépend de la composition et est déterminée par calcul plutôt que par une méthode de mesure de poids. Les valeurs sont calculées en conformité avec la procédure de The Aluminium Association, qui est décrite pages 2-12 et 2.13 de « Aluminum Standards and Data ». Les définitions des états métallurgiques sont indiquées dans la norme européenne EN 515 (2009).Unless otherwise stated, all indications regarding the chemical composition of alloys are expressed as a weight percentage based on the total weight of the alloy. The designation of alloys is done in accordance with The Aluminum regulations. Association, known to those skilled in the art. Density depends on composition and is determined by calculation rather than a weight measurement method. Values are calculated in accordance with The Aluminum Association procedure, which is described on pages 2-12 and 2.13 of “Aluminum Standards and Data”. Definitions of metallurgical conditions are given in European standard EN 515 (2009).

Sauf mention contraire, les caractéristiques mécaniques statiques, en d'autres termes la résistance à la rupture Rm, la limite d'élasticité conventionnelle à 0,2% d'allongement Rp0,2 (« limite d'élasticité ») et l'allongement à la rupture A, sont déterminées par un essai de traction selon la norme EN 10002-1 (2001), le prélèvement et le sens de l'essai étant définis par la norme EN 485-1 (2016).Unless otherwise stated, the static mechanical characteristics, in other words the breaking strength R m , the conventional yield strength at 0.2% elongation R p0.2 (“yield strength”) and l elongation at break A, are determined by a tensile test according to standard EN 10002-1 (2001), the sampling and direction of the test being defined by standard EN 485-1 (2016).

Le facteur d'intensité de contrainte (KQ) est déterminé selon la norme ASTM E 399 (2012). Ainsi, la proportion des éprouvettes définie au paragraphe 7.2.1 de cette norme est toujours vérifiée de même que la procédure générale définie au paragraphe 8. La norme ASTM E 399 (2012) donne aux paragraphes 9.1.3 et 9.1.4 des critères qui permettent de déterminer si KQ est une valeur valide de K1C. Ainsi, une valeur K1C est toujours une valeur KQ la réciproque n'étant pas vraie. Dans le cadre de l'invention, les critères des paragraphes 9.1.3 et 9.1.4 de la norme ASTM E399 (2012) ne sont pas toujours vérifiés, cependant pour une géométrie d'éprouvette donnée, les valeurs de KQ présentées sont toujours comparables entre elles, la géométrie d'éprouvette permettant d'obtenir une valeur valide de K1C n'étant pas toujours accessible compte tenu des contraintes liées aux dimensions des tôles ou profilés.The stress intensity factor (K Q ) is determined according to ASTM E 399 (2012). Thus, the proportion of test pieces defined in paragraph 7.2.1 of this standard is always verified as well as the general procedure defined in paragraph 8. The ASTM E 399 (2012) standard gives paragraphs 9.1.3 and 9.1.4 criteria which allow us to determine whether K Q is a valid value of K 1C . Thus, a K 1C value is always a K Q value, the converse not being true. In the context of the invention, the criteria of paragraphs 9.1.3 and 9.1.4 of standard ASTM E399 (2012) are not always verified, however for a given specimen geometry, the values of K Q presented are always comparable to each other, the specimen geometry making it possible to obtain a valid value of K 1C not always being accessible given the constraints linked to the dimensions of the sheets or profiles.

Sauf mention contraire, les définitions de la norme EN 12258 (2012) s'appliquent. L'épaisseur des profilés est définie selon la norme EN 2066 :2001 : la section transversale est divisée en rectangles élémentaires de dimensions A et B ; A étant toujours la plus grande dimension du rectangle élémentaire et B pouvant être considéré comme l'épaisseur du rectangle élémentaire.Unless otherwise stated, the definitions in EN 12258 (2012) apply. The thickness of the profiles is defined according to standard EN 2066:2001: the cross section is divided into elementary rectangles of dimensions A and B; A always being the largest dimension of the elementary rectangle and B can be considered as the thickness of the elementary rectangle.

On appelle ici « élément de structure » ou « élément structural » d'une construction mécanique une pièce mécanique pour laquelle les propriétés mécaniques statiques et/ou dynamiques sont particulièrement importantes pour la performance de la structure, et pour laquelle un calcul de structure est habituellement prescrit ou réalisé. Il s'agit typiquement d'éléments dont la défaillance est susceptible de mettre en danger la sécurité de ladite construction, de ses utilisateurs, de ses usagers ou d'autrui. Pour un avion, ces éléments de structure comprennent notamment les éléments qui composent le fuselage (tels que la peau de fuselage (fuselage skin en anglais), les raidisseurs ou lisses de fuselage (stringers), les cloisons étanches (bulkheads), les cadres de fuselage (circumferential frames), les ailes (tels que la peau de voilure (wing skin), les raidisseurs (stringers ou stiffeners), les nervures (ribs) et longerons (spars)) et l'empennage composé notamment de stabilisateurs horizontaux et verticaux (horizontal or vertical stabilisers), ainsi que les profilés de plancher (floor beams), les rails de sièges (seat tracks) et les portes.Here we call "structural element" or "structural element" of a mechanical construction a mechanical part for which the static and/or dynamic mechanical properties are particularly important for the performance of the structure, and for which a structural calculation is usually prescribed or carried out. These are typically elements whose failure is likely to endanger the safety of said construction, its users, its users or others. For an aircraft, these structural elements include in particular the elements which make up the fuselage (such as the fuselage skin), the fuselage stiffeners or stringers (stringers), the bulkheads (bulkheads), the fuselage frames. fuselage (circumferential frames), the wings (such as the wing skin), the stiffeners (stringers or stiffeners), the ribs (ribs) and spars (spars)) and the empennage composed in particular of horizontal and vertical stabilizers (horizontal or vertical stabilizers), as well as floor beams, seat tracks and doors.

Les présents inventeurs ont constaté que, de manière surprenante, pour certains alliages AlCuLiMgMnZr de densité particulièrement faible contenant moins de 0,1% en poids d'argent et une addition conjointe de cuivre, lithium, magnésium et manganèse, le choix spécifique d'une teneur particulière en zirconium, fonction de la teneur en lithium, permet d'améliorer de façon très significative la robustesse du procédé de fabrication tout en maintenant pour le produit un compromis satisfaisant entre résistance mécanique et tolérance aux dommages. Par robustesse de procédé de fabrication, on entend ici générant peu de rebuts liés en particulier à des problèmes de fentes à chaud et permettant l'utilisation d'une quantité importante d'alliage recyclé.The present inventors have found that, surprisingly, for certain AlCuLiMgMnZr alloys of particularly low density containing less than 0.1% by weight of silver and a joint addition of copper, lithium, magnesium and manganese, the specific choice of a particular zirconium content, depending on the lithium content, makes it possible to very significantly improve the robustness of the manufacturing process while maintaining for the product a satisfactory compromise between mechanical resistance and tolerance to damage. By robustness of the manufacturing process, we mean here generating little scrap linked in particular to hot slot problems and allowing the use of a significant quantity of recycled alloy.

Le produit en alliage à base d'aluminium selon l'invention comprend, en pourcentage en poids,

  • Cu : 2,4-3,2 ; préférentiellement 2,5-3,0 ;
  • Li : 1,6-2,3 ; préférentiellement 1,7-2,2 ;
  • Mg : 0,3-0,9 ; préférentiellement 0,5-0,7 ;
  • Mn : 0,2 - 0,6 ; préférentiellement 0,3-0,6 ;
  • Zr : 0,13-0,16 ; préférentiellement 0,13-0,16 ; et
    tel que Zr ≥ -0,06*Li + 0,242 ou Zr*Li ≥ 0,235;
  • Zn : < 1,0 préférentiellement <0,9 ;
  • Ag : < 0,15 ; préférentiellement <0,1 ;
  • Fe + Si ≤ 0,20 ;
  • optionnellement au moins un élément parmi Ti, Sc, Cr, Hf et V, la teneur dudit élément, s'il est choisi, étant :
    • Ti : 0,01 - 0,15 ; préférentiellement 0,01-0,05 ;
    • Sc : 0,01 - 0,15, préférentiellement 0,02-0,1 ;
    • Cr : 0,01 - 0,3, préférentiellement 0,02-0,1 ;
    • Hf: 0,01 - 0, 5 ;
    • V : 0,01 - 0,3 ; préférentiellement 0,02-0,1 ;
  • autres éléments ≤ 0,05 chacun et ≤ 0,15 au total, reste aluminium
The aluminum-based alloy product according to the invention comprises, in percentage by weight,
  • Cu: 2.4-3.2; preferably 2.5-3.0;
  • Li: 1.6-2.3; preferably 1.7-2.2;
  • Mg: 0.3-0.9; preferably 0.5-0.7;
  • Mn: 0.2 - 0.6; preferably 0.3-0.6;
  • Zr: 0.13-0.16; preferably 0.13-0.16; And
    such that Zr ≥ -0.06*Li + 0.242 or Zr*Li ≥ 0.235;
  • Zn: <1.0 preferably <0.9;
  • Ag: <0.15; preferably <0.1;
  • Fe + Si ≤ 0.20;
  • optionally at least one element from Ti, Sc, Cr, Hf and V, the content of said element, if chosen, being:
    • Ti: 0.01 - 0.15; preferably 0.01-0.05;
    • Sc: 0.01 - 0.15, preferably 0.02-0.1;
    • Cr: 0.01 - 0.3, preferably 0.02-0.1;
    • Hf: 0.01 - 0.5;
    • V: 0.01 - 0.3; preferably 0.02-0.1;
  • other elements ≤ 0.05 each and ≤ 0.15 in total, remaining aluminum

La teneur en cuivre de l'alliage selon l'invention pour laquelle à la fois le compromis de propriétés et l'amélioration de la faisabilité du procédé sont obtenus est de 2,4 à 3,2 % en poids. Dans un mode de réalisation la teneur en cuivre est de 2,5 à 3,0% en poids et préférentiellement, de 2,6 à 2,9 % en poids. Dans un autre mode de réalisation la teneur en cuivre est de 2,4 à 2,6 % en poids.The copper content of the alloy according to the invention for which both the compromise of properties and the improvement of the feasibility of the process are obtained is 2.4 to 3.2% by weight. In one embodiment the copper content is 2.5 to 3.0% by weight and preferably 2.6 to 2.9% by weight. In another embodiment the copper content is 2.4 to 2.6% by weight.

La teneur en lithium de l'alliage selon l'invention est telle qu'elle permet d'obtenir un produit ayant une densité particulièrement intéressante, notamment une densité inférieure à 2,63 g/cm3, plus particulièrement inférieure à 2,62 g/cm3 et, plus particulièrement encore, inférieure ou égale à 2,61 g/cm3. La teneur en lithium de l'alliage est ainsi supérieure à 1,6% en poids, préférentiellement supérieure à 1,7% en poids et, plus préférentiellement encore, supérieure à 1,9% en poids. Une telle teneur en lithium induit une très forte sensibilité à l'oxydation, à l'hydrogénation et à la fissuration à chaud engendrant des difficultés de coulée de l'alliage et, par conséquent, nécessite des procédés de fabrication tout à fait particuliers. La demande WO2015/086921 décrit notamment le fait que, le lithium étant particulièrement oxydable, la coulée des alliages aluminium-cuivre-lithium génère des sites d'initiation de fissure en fatigue plus nombreux que pour les alliages de type 2XXX sans lithium. Afin de remédier à ce problème, il a été proposé de réaliser la coulée dans des conditions spécifiques, notamment des conditions telles que les teneurs en hydrogène et en oxygène soient maintenues particulièrement basses et que la coulée soit de type semi-vertical utilisant un distributeur particulier. Cependant, pour les teneurs de lithium particulièrement élevées dont il est question ici, il est en outre généralement constaté des problèmes de fente à chaud ou fissuration à coeur de la forme brute lors de la coulée. Pour remédier à ce problème, il est généralement admis de réaliser la coulée à des vitesses particulièrement lentes et, par voie de conséquence, à des températures élevées pour éviter qu'en raison de son faible débit le métal liquide n'atteigne localement des températures suffisamment faibles pour induire la formation de cristaux flottants et d'intermétalliques primaires compte tenu de la forte teneur en éléments péritectiques, en particulier le Zr. Il est alors nécessaire de contrôler de façon particulièrement précise la température du bain de métal liquide lors de la coulée : plus le débit métal est faible, plus la température du métal dans le four de maintien doit être élevée, ce qui entraîne son oxydation exacerbée.The lithium content of the alloy according to the invention is such that it makes it possible to obtain a product having a particularly interesting density, in particular a density less than 2.63 g/cm 3 , more particularly less than 2.62 g /cm 3 and, more particularly, less than or equal to 2.61 g/cm 3 . The lithium content of the alloy is thus greater than 1.6% by weight, preferably greater than 1.7% by weight and, even more preferably, greater than 1.9% by weight. Such a lithium content induces a very high sensitivity to oxidation, hydrogenation and hot cracking, causing difficulties in casting the alloy and, consequently, requires very specific manufacturing processes. Requirement WO2015/086921 describes in particular the fact that, lithium being particularly oxidizable, the casting of aluminum-copper-lithium alloys generates more fatigue crack initiation sites than for type 2XXX alloys without lithium. In order to remedy this problem, it was proposed to carry out the casting under specific conditions, in particular conditions such that the hydrogen and oxygen contents are kept particularly low and that the casting is of the semi-vertical type using a particular distributor. . However, for the particularly high lithium contents in question here, problems of hot splitting or cracking in the core of the raw form during casting are also generally observed. To remedy this problem, it is generally accepted to carry out the casting at particularly slow speeds and, consequently, at high temperatures to prevent, due to its low flow rate, the liquid metal from locally reaching temperatures low enough to induce the formation of floating crystals and primary intermetallics given the high content of peritectic elements, in particular Zr. It is then necessary to control the temperature of the liquid metal bath particularly precisely during casting: the lower the metal flow rate, the higher the temperature of the metal in the holding furnace must be, which leads to its exacerbated oxidation.

Outre un contrôle du compromis entre la température et la vitesse de coulée, il peut être remédié au problème de fissuration à chaud en affinant fortement l'alliage lors de la coulée. Il est en effet connu que le risque de fissuration à chaud est d'autant plus élevé que le grain de coulée est plus grossier. Une réduction de la taille de grains ainsi qu'un changement de la forme des grains peuvent être obtenus en ajoutant de fortes quantités d'agent affinant du grain lors de la coulée. Les agents affinant du grain typiques sont Al3%Ti0.15%C, Al1%Ti0.15%C, Al3%Ti1%B et Al5%Ti1%B sous forme de fil généralement ajouté en ligne. L'addition de ces agents induit la dispersion de fines particules de borure ou de carbure dans le métal liquide qui vont servir de sites de nucléation des grains lors de la solidification. Cependant, l'ajout d'une forte quantité d'agents affinant du grain n'est pas souhaitable en particulier lorsque l'on souhaite pouvoir maintenir un taux de recyclage élevé dans le procédé de fabrication de l'alliage. En effet, l'apport d'agents affinant du grain comprenant du titane ainsi que celui de refontes d'alliages contenant également du titane induit rapidement, au fur et à mesure des cycles de production de l'alliage, une augmentation de la teneur en titane totale de l'alliage, ce qui dégrade les propriétés de tolérance au dommage du produit corroyé et limite ainsi l'apport possible de métal recyclé dans la charge.In addition to controlling the compromise between temperature and casting speed, the problem of hot cracking can be remedied by strongly refining the alloy during casting. It is in fact known that the risk of hot cracking is higher as the casting grain is coarser. A reduction in grain size as well as a change in grain shape can be achieved by adding large amounts of grain refiner during casting. Typical grain refiners are Al3%Ti0.15%C, Al1%Ti0.15%C, Al3%Ti1%B and Al5%Ti1%B in wire form usually added in-line. The addition of these agents induces the dispersion of fine boride or carbide particles in the liquid metal which will serve as grain nucleation sites during solidification. However, the addition of a large quantity of grain refining agents is not desirable, particularly when it is desired to be able to maintain a high recycling rate in the alloy manufacturing process. Indeed, the addition of grain refining agents comprising titanium as well as that of remelting of alloys also containing titanium rapidly induces, as the alloy production cycles progress, an increase in the content of total titanium of the alloy, which degrades the damage tolerance properties of the wrought product and thus limits the possible contribution of recycled metal in the load.

Les présents inventeurs ont mis en évidence, de façon tout à fait surprenante, qu'un alliage AlCuLiMgMnZr selon l'invention, ayant notamment des teneurs en Li et en Zr particulières, permettait d'améliorer la robustesse du procédé de fabrication et de limiter voire de supprimer l'apport en agent affinant du grain.The present inventors have demonstrated, quite surprisingly, that an AlCuLiMgMnZr alloy according to the invention, having in particular particular Li and Zr contents, made it possible to improve the robustness of the manufacturing process and to limit or even to eliminate the supply of grain refining agents.

La teneur en lithium de l'alliage selon l'invention est ainsi supérieure à 1,6% en poids, préférentiellement supérieure à 1,7% en poids et, plus préférentiellement encore, supérieure à 1,9% en poids. Avantageusement la teneur en Li de l'alliage est de 1,7 à 2,3% en poids ou encore de 2,0 à 2,2% en poids. La teneur élevée en lithium exacerbe en particulier la sensibilité à l'oxydation du bain de métal liquide, favorise les problèmes de fissuration à coeur lors de la coulée ce qui nécessite de réduire la vitesse de coulée.The lithium content of the alloy according to the invention is thus greater than 1.6% by weight, preferably greater than 1.7% by weight and, even more preferably, greater than 1.9% by weight. Advantageously the Li content of the alloy is 1.7 to 2.3% by weight or another 2.0 to 2.2% by weight. The high lithium content in particular exacerbates the sensitivity to oxidation of the liquid metal bath and promotes core cracking problems during casting, which requires reducing the casting speed.

La teneur en zirconium est de 0,13 à 0,16% en poids ; et plus préférentiellement de 0,14 à 0,15% en poids.The zirconium content is 0.13 to 0.16% by weight; and more preferably from 0.14 to 0.15% by weight.

Il a ainsi été mis en évidence que pour les teneurs en lithium et zirconium spécifiques précitées, il est possible de fabriquer à l'aide d'un procédé robuste un alliage selon l'invention dont la taille de grains de coulée est particulièrement avantageuse, limitant notamment les risques de fissuration à chaud lors de la coulée.It has thus been demonstrated that for the aforementioned specific lithium and zirconium contents, it is possible to manufacture using a robust process an alloy according to the invention whose casting grain size is particularly advantageous, limiting in particular the risks of hot cracking during casting.

Sans pour autant en déduire une quelconque théorie, les présents inventeurs pensent que la composition d'alliage selon l'invention précisément sélectionnée permet la formation de phases cristallines cubiques Al3Zr et Al3(Zr,Li) qui sont structurellement similaires à la phase métastable Al3Li qui est connue pour précipiter par démixtion de la solution solide lors d'un revenu après mise en solution et trempe mais qui n'est pas censée se former à partir du liquide, la forme stable connue étant la variété tétragonale. La formation de telles phases grâce à la composition de l'alliage spécifiquement sélectionnée pourrait être à l'origine de sites de nucléation des grains lors de la solidification de la forme brute de coulée permettant ainsi la formation d'une structure granulaire extrêmement fine en présence d'une quantité classique d'agent affinant du grain ou permettant de limiter, éventuellement de supprimer, l'apport d'agent affinant du grain lors de la coulée.Without deducing any theory, the present inventors believe that the alloy composition according to the precisely selected invention allows the formation of cubic crystalline phases Al 3 Zr and Al 3 (Zr, Li) which are structurally similar to the phase metastable Al 3 Li which is known to precipitate by demixing of the solid solution during tempering after solution and quenching but which is not supposed to form from the liquid, the known stable form being the tetragonal variety. The formation of such phases thanks to the specifically selected composition of the alloy could be the origin of grain nucleation sites during the solidification of the as-cast form, thus allowing the formation of an extremely fine granular structure in the presence of a conventional quantity of grain refining agent or making it possible to limit, possibly eliminate, the supply of grain refining agent during casting.

Les présents inventeurs ont ainsi mis en évidence un compromis particulier entre les teneurs en zirconium et en lithium tel qu'il permet d'obtenir à la fois un compromis de propriétés satisfaisant pour le produit corroyé et d'améliorer significativement la robustesse du procédé de fabrication dudit produit en alliage AlCuLiMgMnZr, en particulier de l'étape de coulée de ce procédé. Ainsi, la teneur en zirconium de l'alliage selon l'invention est avantageusement telle que Zr ≥ -0,06*Li + 0,242, préférentiellement telle que telle que Zr ≥ -0,06*Li + 0,2575. Dans un autre mode de réalisation, les teneurs en Li et Zr de l'alliage selon l'invention sont telles que Zr*Li ≥ 0,235, préférentiellement Zr*Li ≥ 0,242, plus préférentiellement Zr*Li ≥ 0,275.The present inventors have thus demonstrated a particular compromise between the zirconium and lithium contents such that it makes it possible to obtain both a satisfactory compromise of properties for the wrought product and to significantly improve the robustness of the manufacturing process. of said AlCuLiMgMnZr alloy product, in particular of the casting step of this process. Thus, the zirconium content of the alloy according to the invention is advantageously such that Zr ≥ -0.06*Li + 0.242, preferably such that Zr ≥ -0.06*Li + 0.2575. In another embodiment, the Li and Zr contents of the alloy according to the invention are such that Zr*Li ≥ 0.235, preferably Zr*Li ≥ 0.242, more preferably Zr*Li ≥ 0.275.

La teneur en magnésium est de 0,3 à 0,9% en poids et, de manière préférée, de 0,5 à 0,7% en poids. Le magnésium, dans la composition particulière d'alliage de la présente invention, contribue à favoriser l'obtention d'un grain de coulée fin.The magnesium content is 0.3 to 0.9% by weight and, preferably, 0.5 to 0.7% by weight. Magnesium, in the particular alloy composition of the present invention, helps to promote obtaining a fine casting grain.

La teneur en manganèse est de 0,2 à 0,6% en poids, préférentiellement de 0,3 à 0,6% en poids et, plus préférentiellement encore de 0,4 à 0,5% en poids. Le manganèse permet en particulier d'atteindre un compromis de propriétés satisfaisant pour le produit corroyé.The manganese content is 0.2 to 0.6% by weight, preferably 0.3 to 0.6% by weight and, even more preferably 0.4 to 0.5% by weight. Manganese in particular makes it possible to achieve a satisfactory compromise of properties for the wrought product.

La teneur en argent est inférieure à 0,15% en poids, préférentiellement inférieure à 0,1% en poids et, plus préférentiellement encore inférieure à 0,05% en poids. Les présents inventeurs ont constaté que le compromis avantageux entre la résistance mécanique et la tolérance aux dommages connu pour des alliages contenant typiquement environ 0,3 % en poids d'argent peut être obtenu pour des alliages ne contenant essentiellement pas d'argent avec la sélection de composition effectuée.The silver content is less than 0.15% by weight, preferably less than 0.1% by weight and, more preferably still less than 0.05% by weight. The present inventors have found that the advantageous compromise between mechanical strength and damage tolerance known for alloys typically containing about 0.3% by weight of silver can be obtained for alloys containing essentially no silver with the selection composition carried out.

La teneur en zinc est inférieure à 1,0% en poids, préférentiellement inférieure à 0,9% en poids. Selon un premier mode de réalisation particulier, la teneur en zinc est comprise entre 0,1 et 0,5% en poids et de préférence entre 0,2 et 0,4 % en poids. Selon un second mode de réalisation particulier, la teneur en zinc est inférieure à 0,05% en poids.The zinc content is less than 1.0% by weight, preferably less than 0.9% by weight. According to a first particular embodiment, the zinc content is between 0.1 and 0.5% by weight and preferably between 0.2 and 0.4% by weight. According to a second particular embodiment, the zinc content is less than 0.05% by weight.

L'alliage contient également au moins un élément pouvant contribuer au contrôle de la taille de grain choisi parmi Ti, Cr, Sc, Hf et V, la quantité de l'élément, s'il est choisi, étant de 0,01 à 0,15 % en poids, préférentiellement 0,01 à 0,05% pour Ti, de 0,01 à 0,15 % en poids, préférentiellement 0,02 à 0,1 % en poids pour Sc, de 0,01 à 0,3% en poids et préférentiellement de 0,02 à 0,1 % en poids pour Cr et V et de 0,01 à 0,5 % en poids pour Hf. Selon un mode de réalisation avantageux, on choisit le titane dans les teneurs précitées et encore plus avantageusement dans une teneur allant de 0,01 à 0,03% en poids.The alloy also contains at least one element capable of contributing to grain size control selected from Ti, Cr, Sc, Hf and V, the amount of the element, if chosen, being 0.01 to 0 .15% by weight, preferably 0.01 to 0.05% for Ti, from 0.01 to 0.15% by weight, preferably 0.02 to 0.1% by weight for Sc, from 0.01 to 0 .3% by weight and preferably from 0.02 to 0.1% by weight for Cr and V and from 0.01 to 0.5% by weight for Hf. According to an advantageous embodiment, titanium is chosen in the aforementioned contents and even more advantageously in a content ranging from 0.01 to 0.03% by weight.

Il est préférable de limiter la teneur des impuretés inévitables de l'alliage de façon à atteindre les propriétés de tolérance aux dommages les plus favorables. Les impuretés inévitables comprennent le fer et le silicium, ces impuretés ont une teneur totale inférieure à 0,20 % en poids et de préférence respectivement une teneur inférieure à 0,08 % en poids et 0,06 % en poids pour le fer et le silicium ; les autres éléments sont des impuretés qui ont de préférence une teneur inférieure à 0,05 % en poids chacune et 0,15 % en poids au total.It is preferable to limit the content of unavoidable impurities in the alloy so as to achieve the most favorable damage tolerance properties. The unavoidable impurities include iron and silicon, these impurities have a total content of less than 0.20% by weight and preferably respectively a content of less than 0.08% by weight and 0.06% by weight for iron and silicon. silicon; the other elements are impurities which preferably have a content of less than 0.05% by weight each and 0.15% by weight in total.

Le procédé de fabrication des produits bruts de coulée selon l'invention comprend des étapes d'élaboration, de coulée et de solidification de la forme brute. Ces étapes sont suivies, pour l'élaboration des produits corroyés selon l'invention, des étapes de laminage ou extrusion et/ou forgeage, mise en solution, trempe, détensionnement et optionnellement revenu.The process for manufacturing raw casting products according to the invention comprises stages of preparation, casting and solidification of the raw form. These steps are followed, for the production of the wrought products according to the invention, by the steps of rolling or extrusion and/or forging, solution processing, quenching, stress relief and optionally tempering.

Dans un premier mode de réalisation des produits bruts de coulée, on élabore un bain de métal liquide, on coule une forme brute à partir dudit bain de métal liquide et on réalise une solidification de la forme brute en une billette, une plaque de laminage ou une ébauche de forge. Dans ce premier mode de réalisation, l'étape de coulée est réalisée sans ajout d'affinant du grain ou en ajoutant un affinant comprenant (i) Ti et (ii) bore, B, ou carbone, C, et tel que :

  • la teneur en B provenant de l'agent affinant est inférieure à 45 ppm, préférentiellement inférieure à 20 ppm, préférentiellement inférieure à 10 ppm et, plus préférentiellement encore, inférieure à 5 ppm,
  • la teneur en C est inférieure à 6 ppm, préférentiellement inférieure à 3 ppm, préférentiellement inférieure à 2 ppm et, plus préférentiellement encore, inférieure à 1 ppm.
In a first embodiment of the raw casting products, a bath of liquid metal is produced, a raw form is poured from said bath of liquid metal and the raw form is solidified into a billet, a rolling plate or a forge outline. In this first embodiment, the casting step is carried out without adding a grain refiner or by adding a refiner comprising (i) Ti and (ii) boron, B, or carbon, C, and such that:
  • the B content coming from the refining agent is less than 45 ppm, preferably less than 20 ppm, preferably less than 10 ppm and, even more preferably, less than 5 ppm,
  • the C content is less than 6 ppm, preferably less than 3 ppm, preferably less than 2 ppm and, even more preferably, less than 1 ppm.

Dans un second mode de réalisation des produits bruts de coulée, on élabore un bain de métal liquide, on coule une forme brute à partir dudit bain de métal liquide et on réalise une solidification de la forme brute en une billette, une plaque de laminage ou une ébauche de forge. Dans ce second mode de réalisation, la coulée est réalisée, pour une forme brute de coulée d'épaisseur ou de diamètre D supérieur à 150 mm à une vitesse de coulée v (en mm/min) supérieure à :

  • 30 pour une forme brute de coulée type plaque,
  • 9000/D pour une forme brute de coulée type billette.
In a second embodiment of the raw casting products, a bath of liquid metal is produced, a raw form is poured from said bath of liquid metal and the raw form is solidified into a billet, a rolling plate or a forge outline. In this second embodiment, the casting is carried out, for a raw casting form with a thickness or diameter D greater than 150 mm at a casting speed v (in mm/min) greater than:
  • 30 for a raw plate type casting form,
  • 9000/D for an as-cast billet type form.

Ces deux modes de réalisation peuvent avantageusement être combinés.These two embodiments can advantageously be combined.

De préférence, la taille de grain de l'alliage AlCuLiMgMnZr selon l'invention à l'état brut de coulée, obtenu par l'un des procédés selon l'invention, est inférieure à 110 µm, préférentiellement inférieure ou égale à 105 µm et, plus préférentiellement encore inférieure à 100 µm pour des formes brutes de coulée d'épaisseur ou de diamètre supérieur à 150 mm, de préférence supérieur à 250 mm et préférentiellement encore supérieur à 300 mm. Dans un mode de réalisation en plus préféré, la taille de grain de l'alliage AlCuLiMgMnZr selon l'invention à l'état brut de coulée, obtenu par l'un des procédés selon l'invention, est inférieure ou égale à 95 µm, préférentiellement inférieure 90 µm pour des formes brutes de coulée d'épaisseur ou de diamètre supérieur à 150 mm, de préférence supérieur à 250 mm et préférentiellement encore supérieur à 300 mm.Preferably, the grain size of the AlCuLiMgMnZr alloy according to the invention in the as-cast state, obtained by one of the processes according to the invention, is less than 110 µm, preferably less than or equal to 105 µm and , more preferably even less than 100 µm for raw casting shapes with a thickness or diameter greater than 150 mm, preferably greater than 250 mm and even more preferably greater than 300 mm. In a more preferred embodiment, the grain size of the AlCuLiMgMnZr alloy according to the invention in the as-cast state, obtained by one of the processes according to the invention, is less than or equal to 95 µm, preferably less than 90 µm for as-cast forms with a thickness or diameter greater than 150 mm, preferably greater than 250 mm and even more preferably greater than 300 mm.

La taille de grain de coulée est mesurée, à partir d'échantillons ont été prélevés à mi-rayon (R/2) des billettes, suivant la méthode des intercepts, conformément à la norme ASTM E112. Les produits bruts de coulée selon l'invention permettent l'élaboration de produits corroyés, c'est-à-dire de produits filés, laminés et/ou forgés. Le procédé de fabrication des produits corroyés selon l'invention comprend les étapes de laminage, extrusion et/ou forgeage, mise en solution, trempe, détensionnement et optionnellement revenu en un ou plusieurs paliers. Préférentiellement, les produits corroyés selon l'invention sont des produits filés. Le procédé de fabrication du produit filé selon l'invention comprend les étapes :

  1. a) homogénéisation de la billette ;
  2. b) déformation à chaud et optionnellement à froid de la billette en un produit filé ;
  3. c) mise en solution et trempe dudit produit filé ;
  4. d) optionnellement, traction de façon contrôlée dudit produit filé avec une déformation permanente de 1 à 15%, préférentiellement d'au moins 2% ;
  5. e) optionnellement, revenu à 140 - 170°C pendant 5 à 70 heures.
The casting grain size is measured, from samples taken at mid-radius (R/2) of the billets, following the intercept method, in accordance with ASTM E112. The raw casting products according to the invention allow the production of wrought products, that is to say extruded, rolled and/or forged products. The process for manufacturing the wrought products according to the invention comprises the steps of rolling, extrusion and/or forging, solution processing, quenching, stress relief and optionally tempering in one or more stages. Preferably, the wrought products according to the invention are spun products. The process for manufacturing the spun product according to the invention comprises the steps:
  1. a) homogenization of the billet;
  2. b) hot and optionally cold deformation of the billet into a spun product;
  3. c) dissolving and quenching said spun product;
  4. d) optionally, controlled traction of said spun product with a permanent deformation of 1 to 15%, preferably at least 2%;
  5. e) optionally, returned to 140 - 170°C for 5 to 70 hours.

Les produits selon l'invention peuvent de manière avantageuse être utilisés dans des éléments de structure, en particulier d'avion. Ainsi, un objet de l'invention est un élément de structure incorporant au moins un produit selon l'invention ou un produit fabriqué à partir d'un procédé selon l'invention.The products according to the invention can advantageously be used in structural elements, in particular aircraft. Thus, an object of the invention is a structural element incorporating at least one product according to the invention or a product manufactured using a process according to the invention.

L'utilisation, d'un élément de structure incorporant au moins un produit selon l'invention ou fabriqué à partir d'un tel produit est avantageux, en particulier pour la construction aéronautique. Les produits selon l'invention sont particulièrement avantageux pour la réalisation d'éléments de structure tels que les raidisseurs de fuselage ou de voilure, les poutres de plancher et les rails de siège.The use of a structural element incorporating at least one product according to the invention or manufactured from such a product is advantageous, in particular for aeronautical construction. The products according to the invention are particularly advantageous for the production of structural elements such as fuselage or wing stiffeners, floor beams and seat rails.

Ces aspects, ainsi que d'autres de l'invention sont expliqués plus en détails à l'aide des exemples illustratifs et non limitants suivants.These and other aspects of the invention are explained in more detail using the following illustrative and non-limiting examples.

Exemple 1Example 1

Dans cet exemple, plusieurs billettes en alliage AlCuLiMgMnZr de 384 mm de diamètre ont été coulées. La coulée a été réalisée en présence de 4 kg/tonne d'ATsB, à une vitesse de 25 à 35 mm/min et une température comprise entre 675 et 700°C. La composition des alliages et leur densité sont données dans le tableau 1. Tableau 1 : Composition en % en poids et densité des alliages AlCuLiMgMnZr Alliage Cu Li Mg Zn Ag Mn Zr Ti Densité (g/cm3) AA2196 2,5-3,3 1.4-2.1 0.25-0.8 ≤0.35 0.25-0.6 ≤0.35 0.04-0.18 ≤0.1 2.63 68 3.00 1.67 0.35 0.52 0.02 0.06 0.143 0.040 2.63 69 3.00 1.66 0.33 0.52 0.05 0.31 0.144 0.041 2.63 70 2.55 1.78 0.62 0.52 0.02 0.32 0.146 0.040 2.62 71 2.56 2.00 0.61 0.51 0.02 0.33 0.147 0.038 2.60 72 2.45 1.91 0.63 0.82 0.06 0.32 0.145 0.038 2.61 73 2.52 2.16 0.59 0.60 0.01 0.08 0.124 0.041 2.59 76 2.49 1.93 0.57 0.049 0.03 0.32 0.140 0.038 2.60 Fe + Si ≤ 0,2 % en poids, autres éléments ≤ 0,05 % en poids chacun et ≤ 0,15 % au total In this example, several 384 mm diameter AlCuLiMgMnZr alloy billets were cast. The casting was carried out in the presence of 4 kg/tonne of ATsB, at a speed of 25 to 35 mm/min and a temperature between 675 and 700°C. The composition of the alloys and their density are given in Table 1. Table 1: Composition in % by weight and density of AlCuLiMgMnZr alloys Alloy Cu Li Mg Zn Ag Mn Zr Ti Density (g/cm 3 ) AA2196 2.5-3.3 1.4-2.1 0.25-0.8 ≤0.35 0.25-0.6 ≤0.35 0.04-0.18 ≤0.1 2.63 68 3.00 1.67 0.35 0.52 0.02 0.06 0.143 0.040 2.63 69 3.00 1.66 0.33 0.52 0.05 0.31 0.144 0.041 2.63 70 2.55 1.78 0.62 0.52 0.02 0.32 0.146 0.040 2.62 71 2.56 2.00 0.61 0.51 0.02 0.33 0.147 0.038 2.60 72 2.45 1.91 0.63 0.82 0.06 0.32 0.145 0.038 2.61 73 2.52 2.16 0.59 0.60 0.01 0.08 0.124 0.041 2.59 76 2.49 1.93 0.57 0.049 0.03 0.32 0.140 0.038 2.60 Fe + Si ≤ 0.2% by weight, other elements ≤ 0.05% by weight each and ≤ 0.15% in total

Des échantillons ont été prélevés à mi-rayon (R/2) des billettes afin de mesurer la taille des grains de coulée. La taille des grains de coulée a été mesurée suivant la méthode des intercepts, conformément à la norme ASTM E112. La taille des grains de coulée est donnée dans le tableau 2 ci-après. Les résultats sont présentés dans les figures 1 et 2. Tableau 2 : Taille des grains de coulée des alliages AlCuLiMgMnZr Alliage Taille de grains (µm) AA2196 250 à 320 68 116 69 102 70 105 71 85 72 81 73 120 76 95 Samples were taken at mid-radius (R/2) of the billets to measure the casting grain size. The casting grain size was measured using the intercept method in accordance with ASTM E112. The size of the casting grains is given in Table 2 below. The results are presented in the figures 1 And 2 . Table 2: Casting grain size of AlCuLiMgMnZr alloys Alloy Grain size (µm) AA2196 250 to 320 68 116 69 102 70 105 71 85 72 81 73 120 76 95

Exemple 2Example 2

Dans cet exemple, des billettes en alliage AA2196 (alliage 2 et 5) dont la composition est donnée dans le tableau 3 ci-dessous, ont été homogénéisées 8h à 500 °C puis 24h à 527 °C (alliage 2) ou 8h à 520 °C (alliage 5). Des billettes en alliage 76 de l'exemple 1 ont été homogénéisées 10h à 534°C.In this example, AA2196 alloy billets (alloys 2 and 5) whose composition is given in Table 3 below, were homogenized for 8 hours at 500 °C then 24 hours at 527 °C (alloy 2) or 8 hours at 520 °C (alloy 5). Billets of alloy 76 from Example 1 were homogenized for 10 hours at 534°C.

Après homogénéisation, les billettes ont ensuite été réchauffées à 450 °C +/- 40 °C puis filées à chaud pour obtenir des profilés W selon la figure 3 pour l'alliage 2 et Z selon la figure 4 pour les alliages 5 et 76. Les profilés ainsi obtenus ont été mis en solution à 524 °C, trempés et tractionnés avec un allongement permanent compris entre 2 et 5%. Le revenu a été effectué pendant 48h à 152 °C. Tableau 3 : Composition en % en poids et densité d'alliage AA2196 Alliage Si Fe Cu Mn Mg Zn Ti Zr Li Ag Densité (g/cm3) 2 0,04 0,05 2,83 0,33 0,36 0,02 0,02 0,11 1,59 0,38 2,64 5 0.03 0.04 2,90 0.31 0.40 0.01 0.03 0.1 1,67 0,38 2,64 Autres éléments ≤ 0,05 % en poids chacun et ≤ 0,15 % au total After homogenization, the billets were then reheated to 450 °C +/- 40 °C then hot-spun to obtain W profiles according to the Figure 3 for alloy 2 and Z according to Figure 4 for alloys 5 and 76. The profiles thus obtained were put in solution at 524 °C, quenched and tensile with a permanent elongation of between 2 and 5%. Tempering was carried out for 48 hours at 152°C. Table 3: Composition in % by weight and density of AA2196 alloy Alloy If Fe Cu Mn Mg Zn Ti Zr Li Ag Density (g/cm 3 ) 2 0.04 0.05 2.83 0.33 0.36 0.02 0.02 0.11 1.59 0.38 2.64 5 0.03 0.04 2.90 0.31 0.40 0.01 0.03 0.1 1.67 0.38 2.64 Other elements ≤ 0.05% by weight each and ≤ 0.15% in total

Des échantillons prélevés en fin de profilé ont été testés pour déterminer leurs propriétés mécaniques statiques ainsi que leur ténacité (Kq). La localisation des prélèvements est indiquée en pointillés sur les figures 3 et 4. Les éprouvettes utilisées pour la mesure des propriétés statiques étaient de diamètre 10mm et prélevées de telle sorte que la direction de l'axe de l'éprouvette corresponde à la direction de filage (sens L). Les éprouvettes utilisées pour les mesures de ténacité étaient de type CT et avaient pour caractéristiques B=20 mm et W = 50 mm et ont été usinées de telle façon que la direction de chargement corresponde à la direction de filage et la direction de propagation soit perpendiculaire à la direction de filage et contenue dans le plan des figures 3 et 4 (configuration L-T).Samples taken at the end of the profile were tested to determine their static mechanical properties as well as their toughness (K q ). The location of the samples is indicated in dotted lines on the figures 3 And 4 . The test pieces used for measuring the static properties were 10 mm in diameter and taken in such a way that the direction of the axis of the test piece corresponds to the spinning direction (direction L). The specimens used for the toughness measurements were of type CT and had the characteristics B = 20 mm and W = 50 mm and were machined in such a way that the direction of loading corresponds to the direction of spinning and the direction of propagation is perpendicular to the spinning direction and contained in the plan of the figures 3 And 4 (LT configuration).

Les résultats obtenus sont présentés dans le tableau 4. Tableau 4 : Limite d'élasticité Rp0.2 (L) en MPa et ténacité Kq (L-T) en MPaVm Alliage Rp0.2(L) Kq (L-T) 2 522 37.6 5 536 38.2 76 512 43.4 The results obtained are presented in Table 4. Table 4: Yield strength Rp0.2 (L) in MPa and toughness Kq (LT) in MPaVm Alloy Rp0.2(L) Kq (LT) 2 522 37.6 5 536 38.2 76 512 43.4

Exemple 3Example 3

Différents alliages dont la composition particulière est détaillée dans le tableau 5 ont été solidifiés sous forme de pions expérimentaux selon la norme éditée par The Aluminium Association « TP-1 / Standard Test Procedure for Aluminum Alloy Grain Refiners » (2012 ). Les pions ont ainsi été obtenus par solidification de l'alliage liquide dans des louches en acier doux d'épaisseur 3 mm.Different alloys whose particular composition is detailed in Table 5 were solidified in the form of experimental pawns according to the standard published by The Aluminum Association “TP-1 / Standard Test Procedure for Aluminum Alloy Grain Refiners” (2012 ). The pawns were thus obtained by solidification of the liquid alloy in mild steel ladles 3 mm thick.

Pour ce faire, un bain de métal liquide a été réalisé dans un four de fusion, la composition du métal liquide est celle des alliages solidifiés, la solidification ultérieure étant réalisée sans l'ajout classique d'affinant de façon à mettre en évidence la contribution intrinsèque de la composition de l'alliage à la loi de germination. Les tailles de grains obtenues sont différentes de celles obtenues en coulée verticale en présence d'affinant, mais la possibilité d'auto-inoculation de l'alliage dans un certain domaine de composition peut être mise en évidence par ce test qui permet ainsi de préciser la position de la frontière du domaine d'intérêt dans le plan Zr vs Li. Au niveau de la surface étudiée détaillée ci-après, la vitesse de refroidissement est de 3,5K.s-1.To do this, a bath of liquid metal was produced in a melting furnace, the composition of the liquid metal is that of the solidified alloys, the subsequent solidification being carried out without the conventional addition of refining agent so as to highlight the contribution intrinsic to the composition of the alloy to the law of germination. The grain sizes obtained are different from those obtained in vertical casting in the presence of refining agent, but the possibility of self-inoculation of the alloy in a certain composition range can be demonstrated by this test which thus makes it possible to specify the position of the boundary of the domain of interest in the Zr vs Li plane. At the surface studied detailed below, the cooling rate is 3.5K.s -1 .

A refroidissement complet, le pion, qui a la forme d'un tronçon de cône de hauteur 65mm et dont les bases circulaires ont des rayons respectifs de 25mm et 65mm, est démoulé et découpé selon son axe. La mesure de grain est effectuée à 38 mm de la petite face.When completely cooled, the pawn, which has the shape of a section of cone 65mm high and whose circular bases have respective radii of 25mm and 65mm, is demolded and cut along its axis. The grain measurement is carried out 38 mm from the small face.

La partie supérieure du pion ainsi découpé a été polie puis a subi une oxydation anodique avant d'être observée sous lumière polarisée. La taille de grain a été mesurée sur cette partie supérieure ainsi préparée par une méthode d'intercept selon la norme ASTM El12.The upper part of the pawn thus cut out was polished then underwent anodic oxidation before being observed under polarized light. The grain size was measured on this upper part thus prepared by an intercept method according to the ASTM El12 standard.

La taille de grain est présentée dans le tableau 5 et sur les Figures 5 et 6. Tableau 5 : Composition en % en poids et densité de l'alliage AlCuLiMgMnZr utilisé Alliage Si Fe Cu Mn Mg Ti Li Zr Taille de grains (%) (%) (%) (%) (%) (%) (%) (%) (µm) 1 0.02 0.037 3.22 0.31 0.37 0.03 1.80 0.101 823 2 0.02 0.039 3.25 0.31 0.36 0.03 1.91 0.101 1017 3 0.02 0.039 3.31 0.31 0.38 0.03 2.07 0.101 913 4 0.02 0.038 3.26 0.31 0.37 0.03 1.83 0.115 927 5 0.02 0.038 3.25 0.31 0.37 0.03 1.93 0.120 799 6 0.02 0.039 3.31 0.31 0.36 0.03 2.07 0.116 698 8 0.02 0.040 3.3 0.31 0.50 0.03 2.08 0.122 490 10 0.02 0.039 3.21 0.31 0.33 0.03 1.79 0.136 484 11 0.02 0.040 3.25 0.30 0.33 0.03 1.87 0.136 519 12 0.03 0.042 3.21 0.30 0.33 0.03 1.99 0.139 422 Fe + Si ≤ 0,2 % en poids, autres éléments ≤ 0,05 % en poids chacun et ≤ 0,15 % au total The grain size is presented in Table 5 and on the Figures 5 And 6 . Table 5: Composition in % by weight and density of the AlCuLiMgMnZr alloy used Alloy If Fe Cu Mn Mg Ti Li Zr Grain size (%) (%) (%) (%) (%) (%) (%) (%) (µm) 1 0.02 0.037 3.22 0.31 0.37 0.03 1.80 0.101 823 2 0.02 0.039 3.25 0.31 0.36 0.03 1.91 0.101 1017 3 0.02 0.039 3.31 0.31 0.38 0.03 2.07 0.101 913 4 0.02 0.038 3.26 0.31 0.37 0.03 1.83 0.115 927 5 0.02 0.038 3.25 0.31 0.37 0.03 1.93 0.120 799 6 0.02 0.039 3.31 0.31 0.36 0.03 2.07 0.116 698 8 0.02 0.040 3.3 0.31 0.50 0.03 2.08 0.122 490 10 0.02 0.039 3.21 0.31 0.33 0.03 1.79 0.136 484 11 0.02 0.040 3.25 0.30 0.33 0.03 1.87 0.136 519 12 0.03 0.042 3.21 0.30 0.33 0.03 1.99 0.139 422 Fe + Si ≤ 0.2% by weight, other elements ≤ 0.05% by weight each and ≤ 0.15% in total

Claims (13)

  1. Product made of alloy containing aluminum comprising, in % by weight,
    Cu: 2.4-3.2; preferably 2.5-3.0;
    Li: 1.6-2.3; preferably 1.7-2.2;
    Mg: 0.3-0.9; preferably 0.5-0.7;
    Mn: 0.2 - 0.6; preferably 0.3-0.6;
    Zr: 0.13 - 0.16; preferably 0.13-0.15; and
    such that Zr ≥ -0.06*Li + 0.242 or Zr*Li ≥ 0.235,
    Zn: < 1.0 preferably <0.9;
    Ag: < 0.15; preferably <0.1;
    Fe + Si ≤ 0.20;
    optionally at least one element out of Ti, Sc, Cr, Hf and V, the concentration of the element if it is chosen, being:
    Ti: 0.01 - 0.15; preferably 0.01-0.05;
    Sc: 0.01 - 0.15, preferably 0.02-0.1;
    Cr: 0.01 - 0.3, preferably 0.02-0.1;
    Hf: 0.01 - 0. 5;
    V: 0.01 - 0.3, preferably 0.02-0.1;
    other elements ≤ 0.05 each and ≤ 0.15 in total, the rest aluminum
  2. Product according to claim 1, wherein the concentration of lithium is from 2.0 to 2.2% by weight.
  3. Product according to any one of claims 1 to 2, wherein the concentration of manganese is from 0.4 to 0.5% by weight.
  4. Product according to any one of claims 1 to 3, wherein the concentration of zirconium is from 0.14 to 0.15% by weight.
  5. Product according to any one of claims 1 to 4, wherein the concentration of zirconium is such that Zr ≥ -0.06*Li + 0.2575 or the concentrations of zirconium and lithium are such that Zr*Li ≥ 0.275.
  6. Product according to any one of claims 1 to 5, wherein the concentration of titanium is between 0.01 and 0.03% by weight.
  7. Method for manufacturing an as-cast product made of aluminum alloy according to any one of claims 1 to 6, comprising the steps of:
    a) producing a bath of liquid metal;
    b) casting an unwrought product from said bath of liquid metal;
    c) solidifying the unwrought product into a billet, a rolling ingot or a forging blank;
    characterized in that the casting is carried out without addition of a grain refiner or while adding a refiner comprising (i) Ti and (ii) B or C and such that the concentration of B coming from the refining agent is less than 45ppm, preferably less than 20ppm and, even more preferably, less than 10ppm and that of C less than 6ppm, preferably less than 3ppm and, even more preferably, less than 2ppm.
  8. Method for manufacturing an as-cast product made of aluminum alloy according to any one of claims 1 to 6, comprising the steps of:
    a) producing a bath of liquid metal;
    b) casting an unwrought product from said bath of liquid metal;
    c) solidifying the unwrought product into a billet, a rolling ingot or a forging blank;
    characterized in that the casting is carried out, for an unwrought casting product having a thickness E or having a diameter D greater than 150mm at a casting speed v, in mm/min, greater than:
    - 30 for an unwrought casting product of the plate type,
    - 9000/D for an unwrought casting product of the billet type.
  9. As-cast product having a thickness or having a diameter greater than 150mm, preferably greater than 250mm and more preferably greater than 300mm, obtained by the method according to claim 7 or claim 8, characterized in that its grain size is less than 110µm, preferably less than or equal to 105µm and, even more preferably less than 90µm.
  10. Method for manufacturing a worked product comprising the steps of manufacturing an as-cast product according to claims 7 and 8 and steps of rolling or extrusion and/or forging, solution heat treatment, quenching, stress relief and optionally aging.
  11. Manufacturing method according to claim 10, comprising the casting of a billet and the steps of:
    a) homogenizing of the billet;
    b) extrusion of the billet into an extruded product;
    c) solution heat treatment and quenching of said extruded product;
    d) stretching in a controlled manner of said extruded product with a permanent set of 1 to 15%, preferably of at least 2%;
    e) aging of said extruded product by heating to 140 to 170°C for 5 to 70 hours.
  12. Structural element incorporating at least one product obtained by the method according to claim 11 or manufactured from a product according to any one of claims 1 to 6.
  13. Structural element according to claim 12, characterized in that it is used for the manufacturing of airplane-wing lower-surface or upper-surface elements, preferably stiffeners, spars and ribs, or of fuselage elements such as stiffeners or frames, or elements of inner structure such as floor beams or seat rails.
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