Classifications

• • 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
• • 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

Definitions

• the invention generally relates to wrought products 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 interesting in this respect, since 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, in particular in terms of a compromise between the static mechanical strength properties (elastic limit, breaking strength) and the properties of damage tolerance ( toughness, resistance to the propagation of fatigue cracks), these properties being in general antinomic.
• These alloys must also have sufficient corrosion resistance, be able to be shaped according to the usual methods and have low residual stresses so that they can be machined integrally.
• No. 5,032,359 discloses a broad 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 under the trade name "Weldalite TM".
• US Patent 5,198,045 discloses a family of Weldalite TM alloys comprising (in% by weight) (2,4-3,5) Cu, (1,35-1, S) Li, (0.25-0.65) Mg, (0.25-0.65) Ag, (0.08-0.25) Zr.
• the wrought products made with these alloys combine a density of less than 2.64 g / cm 3 and a compromise between strength and toughness of interest.
• US Pat. No. 7,229,509 describes a family of Weldalite TM alloys comprising (in% 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, (up to 0.4) Zr or other affinants such as Cr, Ti, Hf, Sc and V. Examples presented have a compromise between mechanical strength and improved toughness but their density is greater than 2.7 g / cm 3 .
• Patent application WO2007 / 080267 discloses a Zirconium-free Weldalite TM alloy for fuselage plates 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.
• Patent EP1891247 discloses a Weldalite TM alloy which is lightly loaded with alloying elements and is also intended for the manufacture of fuselage sheets comprising (in% by weight) (2.7-3.4) Cu, (0.8-1, 4) Li, (0.2-0.6) Mg, (0, 1-0.8) Ag and at least one element selected from Zr, Mn, Cr, Sc, Hf, Ti.
• Patent Application WO2006 / 131627 discloses an alloy for fuselage plates comprising (in% by weight) (2.7-3.4) Cu, (0.8-1.4) Li, (0.2- 0.6) Mg, (0.1-0.8) Ag and at least one of Zr, Mn, Cr, Sc, Hf and Ti, wherein the Cu and Li contents are Cu + 5 / 3 Li ⁇ 5.2.
• No. 5,455,003 discloses a process for producing aluminum-copper-lithium alloys having improved mechanical strength and toughness properties at cryogenic temperature. This method applies in particular to an alloy comprising (in% by weight) (2.0-6.5) Cu, (0.2-2.7) Li, (0-4.0) Mg, (0- 4.0) Ag, (0-3.0) Zn.
• AA2196 alloy comprising (in% by weight) (2.5-3.3) Cu, (1.4-2.1) Li, (0.25-0.8) Mg, is also known. , 25-0.6) Ag, (0.04-0.18) Zr and at most 0.35 Mn.
• the subject of the invention is a process for manufacturing a spun, rolled and / or forged product based on aluminum alloy in which: a) a bath of liquid metal comprising 2.0 to 3.5% is produced; by weight of Cu, 1, 4 to 1.8% by weight of Li, 0.1 to 0.5% by weight of Ag, 0.1 to 1.0% by weight of Mg, 0.05 to 0 , 18% by weight of Zr, 0.2 to 0.6% by weight of Mn and at least one element selected from Cr, Sc, Hf and Ti, the amount of said element, if selected, being 0, 0.5 to 0.3% by weight for Cr and Sc, 0.05 to 0.5% by weight for Hf and from 0.01 to 0.15% by weight for Ti, the remainder being aluminum and unavoidable impurities; b) pouring a raw form from said bath of liquid metal; c) homogenizing said crude form at a temperature of between 515 ° C. and
• T in Kelvin
• T ref is a reference temperature set at 793 K
• the solution is dissolved and quenched
• an income of said product is obtained by heating at 140 to 170 ° C. for 5 to 70 hours so that said product has a conventional yield strength measured at 0.2% elongation of at least 440 MPa and preferably at least 460 MPa.
• the invention also relates to a product spun, rolled and / or forged aluminum alloy with a density of less than 2.67 g / cm 3 obtainable by the process according to the invention.
• Yet another object of the invention is a structural element incorporating at least one product according to the invention.
• Figure 1 Form of the profile W of Example 1. The dimensions are given in mm. The samples used for the mechanical characterizations were taken from the area indicated by the dots. The thickness of the sole is 16 mm.
• Figure 3 Form Y profile of Example 2. The dimensions are given in mm. The thickness of the sole is 18 mm. Figure 4. Compromise between toughness and mechanical strength obtained for the X profiles of Example 2.
• Figure 7. Form Z profile of Example 3. The dimensions are given in mm. The samples used for the mechanical characterizations were taken from the area indicated by the dots. The thickness of the sole is 20 mm.
• Figure 8. Form of the profile P of Example 4. The dimensions are given in mm.
• Figure 9. Form of the profile Q of Example 5. The dimensions are given in mm.
• alloys are in accordance with the regulations of The Aluminum Association, known to those skilled in the art.
• the density depends on the composition and is determined by calculation rather than by a method of measuring weight.
• the values are calculated in accordance with the procedure of The Aluminum Association, which is described on pages 2-12 and 2.13 of "Aluminum Standards and Data".
• the definitions of the metallurgical states are given in the European standard EN 515.
• the static mechanical characteristics in other words the ultimate tensile strength R m , the conventional yield stress at 0.2% elongation R p0i2 ("yield strength") and elongation at break A, are determined by a tensile test according to EN 10002-1, the sampling and the direction of the test being defined by EN 485-1.
• the stress intensity factor (K Q ) is determined according to ASTM E 399.
• ASTM E 399 gives in 9.1.3 and 9.1.4 criteria to determine if K Q is a valid value of Kic-
• a Kic value is always a value K Q the reciprocal is not true.
• the criteria of paragraphs 9.1.3 and 9.1.4 of ASTM E399 are not always checked, however for a given specimen geometry, the K Q values presented are always comparable to each other. , the specimen geometry to obtain a valid value of Kic is not always accessible given the constraints related to the dimensions of the sheets or profiles.
• the ASTM Acetic Acid Sait Intermittent Spray (MASTMAASIS) test is performed according to ASTM G85.
• the thickness of the profiles is defined according to EN 2066: 2001: the cross section is divided into elementary rectangles of dimensions A and B; A being always the largest dimension of the elementary rectangle and B can be considered as the thickness of the elementary rectangle. The sole is the elementary rectangle with the largest dimension A.
• a "structural element” or “structural element” of a mechanical construction is called 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 realized.
• These are typically elements whose failure is likely to endanger the safety of said construction, its users, its users or others.
• these structural elements include the elements that make up the fuselage (such as fuselage skin (fuselage skin in English), stiffeners or stringers, bulkheads, fuselage (circumferential frames), wings (such as wing skin), stiffeners (stiffeners), ribs (ribs) and spars) and empennage including horizontal stabilizers and vertical stabilizers horizontal or vertical stabilizers, as well as floor beams, seat tracks and doors.
• fuselage such as fuselage skin (fuselage skin in English), stiffeners or stringers, bulkheads, fuselage (circumferential frames), wings (such as wing skin), stiffeners (stiffeners), ribs (ribs) and spars
• empennage including horizontal stabilizers and vertical stabilizers horizontal or vertical stabilizers, as well as floor beams, seat tracks and doors.
• the method according to the invention allows the manufacture of a product spun, rolled and / or forged.
• a bath of liquid metal is produced so as to obtain an aluminum alloy of defined composition.
• the copper content of the alloy for which the surprising effect related to the choice of homogenization conditions is observed is between 2.0 and 3.5% by weight, preferably between 2.45 or 2.5 and 3.3% by weight. In an advantageous embodiment, the copper content is between 2.7 and 3.1% by weight.
• the lithium content is between 1.4 and 1.8%. In an advantageous embodiment, the lithium content is between 1.42 and 1.77% by weight.
• the silver content is between 0.1 and 0.5% by weight. The present inventors have found that a significant amount of silver is not needed to achieve the desired improvement in the trade-off between strength and damage tolerance. In an advantageous embodiment of the invention, the silver content is between 0.15 and 0.35% by weight. In one embodiment of the invention, which has the advantage of minimizing the density, the silver content is at most 0.25% by weight.
• the magnesium content is between 0.1 and 1.0% by weight and preferably it is less than 0.4% by weight.
• the combination of specific homogenization conditions and the simultaneous addition of zirconium and manganese is an essential feature of the invention.
• the zirconium content must be between 0.05 and 0.18% by weight and the manganese content must be between 0.2 and 0.6% by weight.
• the manganese content is at most 0.35% by weight.
• the alloy also contains at least one element that can contribute to the control of the grain size selected from Cr, Sc, Hf and Ti, the quantity of the element, if it is chosen, being 0.05 to 0.3% by weight for Cr and for Sc, 0.05 to 0.5% by weight for Hf and 0.01 to 0.15% by weight for Ti.
• the unavoidable impurities include iron and silicon, these impurities preferably have a content of less than 0.08% by weight and 0.06% by weight for iron and silicon, respectively, the other impurities preferably have a lower content to 0.05% by weight each and 0.15% by weight in total.
• the zinc content is preferably less than 0.04% by weight.
• the composition is adjusted so as to obtain a density at room temperature of less than 2.67 g / cm 3 , even more preferably less than 2.66 g / cm 3, in some cases even less than 2.65 g / cm 3 or even 2.64 g / cm 3 .
• the decrease in density is generally associated with a degradation of the properties. In the context of the invention, it is possible surprisingly to combine a low density with a compromise of very advantageous mechanical properties.
• the liquid metal bath is then cast in a raw form, such as a billet, a rolling plate or a forging blank.
• the crude form is then homogenized at a temperature of between 515 ° C. and 525 ° C. so that the equivalent time t (eq) at 520 ° C. for homogenization is between 5 and 20 hours and preferably between 6 and 20 hours. and 15 hours.
• the equivalent time t (eq) at 520 ° C. is defined by the formula: where T (in Kelvin) is the instantaneous treatment temperature, which changes with time t (in hours), and T ref is a reference temperature set at 793 K. t (eq) is expressed in hours.
• T (in Kelvin) is the instantaneous treatment temperature, which changes with time t (in hours)
• T ref is a reference temperature set at 793 K.
• t (eq) is expressed in hours.
• the homogenization temperature is about 520 0 C and the treatment time is between 8 and 20 hours.
• the times indicated correspond to times for which the metal is actually at the desired temperature.
• the homogenization conditions according to the invention make it possible to improve, surprisingly, the compromise between toughness and mechanical strength with respect to conditions in which the combination of duration and temperature is lower or higher. It is generally accepted by those skilled in the art that, in order to minimize the homogenization time, it is advantageous to carry out the homogenization at the highest possible temperature so as to avoid local melting so as to accelerate the scattering of elements and precipitation of dispersoids.
• the present inventors have found on the contrary for the alloy composition according to the invention, a surprising favorable effect of a combination of duration and homogenization temperature lower than that according to the prior art.
• the raw form is generally cooled to room temperature before being preheated for hot deformation.
• Preheating aims to achieve a temperature preferably between 400 and 500 ° C and preferably of the order of 450 0 C allowing the deformation of the raw form.
• Preheating is typically 20 hours at 520 ° C for plates.
• the times and temperatures mentioned for preheating correspond to the time spent in the oven and the temperature of the oven and not to the temperature actually reached by the metal and the time spent in this oven. temperature.
• induction preheating is advantageous.
• Hot deformation and optionally cold deformation is typically performed by spinning, rolling and / or forging to obtain a spun, rolled and / or forged product.
• the product thus obtained is then put in solution preferably by heat treatment between 490 and 530 ° C for 15 min to 8 h, then typically quenched with water at room temperature or preferably cold water.
• the product then undergoes a controlled pull of 1 to 5% and preferably of at least 2%.
• cold rolling is carried out with a reduction of between 5% and 15% before the controlled pulling step.
• Known steps such as planing, straightening, shaping may optionally be performed before or after the controlled pull.
• An income is produced at a temperature between 140 and 170 0 C for 5 to 70 hours so that the product has a conventional yield strength measured at 0.2% an elongation of at least 440 MPa and preferably at least 460 MPa.
• the present inventors have found that, surprisingly, the combination of the homogenization conditions according to the invention with a preferred income achieved by heating at 148 to 155 ° C. for 10 to 40 hours makes it possible in certain cases to reach a level of toughness. Kic (LT) particularly high.
• the present inventors believe that the products obtained by the process according to the invention have a very particular microstructure, although they have not yet been able to describe it precisely.
• the size, the distribution and the morphology of the dispersoids containing manganese seem to be remarkable for the products obtained by the process according to the invention, however the complete characterization of its dispersoids, whose size is of the order of 50 to 100 nm, requires observations in electron microscopy at a magnification of x 30 000, quantified and numerous which explains the difficulty of obtaining a reliable description.
• the products according to the invention preferably have a substantially non-recrystallized granular structure. By essentially non-recrystallized it is understood that at least 80% and preferably at least 90% of the grains are not recrystallized at quarter and mid-product thickness.
• the spun products and in particular the extruded profiles obtained by the process according to the invention are particularly advantageous.
• the advantages of the method according to the invention have been observed for thin sections whose thickness of at least one elementary rectangle is between 1 mm and 8 mm and thick sections, however the thick sections, that is to say ie whose thickness of at least one elementary rectangle is greater than 8 mm, and preferably greater than 12 mm, or even 15 mm are the most advantageous.
• the compromise between the static mechanical strength and the toughness or the fatigue strength is particularly advantageous for the spun products according to the invention.
• An aluminum alloy spun product according to the invention has a density of less than 2.67 g / cm 3 , is obtainable by the process according to the invention, and is advantageously characterized in that: (a) its conventional yield strength measured at 0.2% elongation in the LR p oj2 (L) direction expressed in MPa and its Kic toughness (LT), in the LT direction expressed in MPa Vin are such that K Q (LT)> 129 to 0.17 R p o, 2 (L), preferential iement K Q (LT)> 132 to 0.17 R p0, 2 (L) and even more preferably iement K Q (LT)> 135 to 0.17 R p o, 2 (L); and or
• T in the LT direction expressed in MPaVm are such that K Q (LT)> 88 - 0.09 R m (TL), preferentially K Q (LT)> 90 - 0.09 R 171 (TL) and even more preferably K Q (LT)> 92 - 0.09 R 171 (TL) and / or
• the tenacity K Q (LT) of the spun products according to the invention is at least
• the density of the spun products according to the invention is less than 2.66 g / cm 3 , more preferably less than 2.65 g / cm 3 and in some cases less than 2.64 g / cm 3 .
• an income is obtained which makes it possible to obtain a conventional yield strength measured at 0.2% elongation greater than 520 MPa, for example from 30 to 152 ° C.
• the resistance at break in the direction LR m (L), expressed in MPa and the toughness K Q (LT), in the direction LT expressed in MPa Vm are then such that R m (L)> 550 and K Q (LT)> 50 .
• the process according to the invention also makes it possible to obtain advantageous rolled products.
• the sheets whose thickness is at least 10 mm and preferably at least 15 mm and / or at most 100 mm and preferably at most 50 mm are advantageous.
• An aluminum alloy laminated product according to the invention has a density of less than 2.67 g / cm 3 , is obtainable by the method according to the invention, and is advantageously characterized in that its tenacity K Q (LT), in the LT direction is at least 23 MPa Vin and preferably at least 25 MPa Vin, its conventional yield strength measured at 0.2% elongation in the LR p o 2 direction ( L) is at least 560 MPa and preferably at least 570 MPa and / or its breaking strength in the LR m (L) direction is at least 585 MPa and preferably at least 595 MPa .
• LT tenacity K Q
• L conventional yield strength measured at 0.2% elongation in the LR p o 2 direction
• L is at least
• the density of the rolled products according to the invention is less than 2.66 g / cm 3 , even more preferably less than 2.65 g / cm 3, in some cases even less than 2.64 g / cm 3. 3 .
• the products according to the invention can advantageously be used in structural elements, in particular aircraft.
• a structural element incorporating at least one product according to the invention or made from such a product is advantageous, in particular for aeronautical construction.
• a structural element, formed of at least one product according to the invention, in particular a spun product according to the invention used as stiffener or frame, can be advantageously used for the manufacture of fuselage panels or airplane wing as well as any other use where the present properties could be advantageous.
• the corrosion resistance of the products of the invention is generally high; for example, the MASTMAASIS test result is at least EA and preferably P for the products according to the invention.
• the plates were homogenized according to the prior art for 8 h at 500 ° C. and then 24h at 527 ° C. Bills were taken from the plates. The billets were heated to 450 ° C. +/- 40 ° C. and then hot-spun to obtain profiles W according to FIG. 1. The profiles thus obtained were dissolved at 524 ° C., quenched with distilled water. temperature below 40 ° C, and tractionned with a permanent elongation of between 2 and 5%. The income was carried out for 48 hours at 152 ° C.
• Table 3 Composition in% by weight and density of the Al-Cu-Li alloy used.
• the billets were homogenized, ie 8 h at 500 ° C. and then 24h at 527 ° C. (reference A) or 8 h at 520 ° C. (reference B) or 8 h at 500 ° C. (reference C).
• the rate of rise in temperature was 15 ° C / h for the homogenization and the equivalent time was 37.5 hours for homogenization of reference A, 9.5 hours for homogenization of reference B, and 4 hours homogenization reference C.
• the billets were heated to 450 0 C +/- 40 0 C and then hot spun to obtain X profiles according to Figure 2 or Y according to Figure 3.
• Example 2 two of the homogenization conditions of Example 2 were compared for another type of profile, obtained from billets taken from a plate whose composition is given in Table 6 below: Table 6. Composition in% by weight of Al-Cu-Li alloys used
• the alloy billets 4 were homogenized for 8 hours at 500 ° C. and then 24h at 527 ° C. (ie the reference homogenization A) while the alloy billets 5 were homogenized for 8 hours at 520 ° C. (reference B). After homogenization, the billets were heated to 450 0 C +/- 40 0 C and then hot spun to obtain Z profiles according to Figure 7. The profiles thus obtained were dissolved at 524 +/- 2 0 C, soaked with water of temperature below 40 0 C, and tractioncolo with a permanent elongation of between 2 and 5%. The profiles finally received an income of 48h at 152 ° C.
• Table 8 Composition in% by weight and density of the Al-Cu-Li alloy used.
• the alloy billets 6 were homogenized for 8 hours at 520 ° C. (ie reference homogenization B). After homogenization, the billets were heated to 450 ° C. +/- 40 ° C. and then hot-spun to obtain P-profiles according to FIG. 8. The profiles thus obtained were dissolved, quenched with water of temperature less than 40 ° C, and tractionned with a permanent elongation of between 2 and 5%. The profiles finally received an income of 48h at 152 ° C. Samples taken at the end of the profile were tested to determine their static mechanical properties (elastic limit R p o , 2 , the breaking strength R m , and elongation at break A).
• Table 11 Composition in% by weight and density of the Al-Cu-Li alloy used.
• the alloy billets 7 were homogenized for 8 hours at 520 ° C. (ie reference homogenization B). After homogenization, the billets were heated to 450 ° C. +/- 40 ° C. and then hot-spun to obtain profiles Q according to FIG. 9. The profiles thus obtained were put in solution, quenched with water of temperature less than 40 ° C, and tractionned with a permanent elongation of between 2 and 5%. The profiles finally had an income of 48h at 152 ° C. Samples taken at the end of the section were tested for their static mechanical properties (elastic limit R p0; 2 , the ultimate strength R m , and the elongation at break A).
• Table 14 Composition in% by weight and density of the Al-Cu-Li alloy used.
• the plate was scalped and then homogenized at 520 +/- 5 0 C for 8 h (the reference homogenization B). After homogenization, the plate was hot rolled to obtain sheets having a thickness of 25 mm. The sheets were put in solution to
• the sheets have an industrial income of 48 h at 152 ° C.
• the results of the mechanical tests (sampling at mid-thickness) carried out on the sheets thus obtained are given in Table 16.
• the homogenization conditions according to the invention were used for two types of profiles, obtained from billets made of two different alloys whose composition is given in Table 17 below.
• Table 17 Composition in% by weight and density of the Al-Cu-Li alloy used.
• the billets were homogenized for 8 hours at 520 ° C. (reference B). The temperature rise rate was 15 ° C./h for homogenization and the equivalent time was 9.5 hours. After homogenization, the billets were reheated to 450 ° C. 0 C +/- 40 0 C and then hot spun to obtain X profiles according to Figure 2 or Y according to Figure 3. The profiles thus obtained were dissolved at 524 +/- 2 0 C, quenched with water. water temperature below 40 ° C, and trapped with a permanent elongation of between 2 and 5%. Different income conditions have been implemented.
• the compromise between toughness and mechanical strength obtained with the alloys 9 and 10 is particularly advantageous, in particular to obtain very high toughness values, with K Q (LT) greater than 50 MPaVm, and even greater than 55 MPaVm.

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