EP1492895B1 - Produits en alliages al-zn-mg-cu - Google Patents

Produits en alliages al-zn-mg-cu Download PDF

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Publication number
EP1492895B1
EP1492895B1 EP03740568A EP03740568A EP1492895B1 EP 1492895 B1 EP1492895 B1 EP 1492895B1 EP 03740568 A EP03740568 A EP 03740568A EP 03740568 A EP03740568 A EP 03740568A EP 1492895 B1 EP1492895 B1 EP 1492895B1
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Prior art keywords
alloy
elements
product according
mpa
content
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Revoked
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EP03740568A
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German (de)
English (en)
French (fr)
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EP1492895A2 (fr
Inventor
Timothy Warner
Christophe Sigli
Bernard Bes
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Constellium Issoire SAS
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Alcan Rhenalu SAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • 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
    • C22F1/053—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 zinc as the next major constituent

Definitions

  • the present invention relates to alloys of Al-Zn-Mg-Cu type with compromised static mechanical characteristics - improved damage tolerance, with a Zn content greater than 8.3%, as well as structural elements for aeronautical construction incorporating half wrought products made from these alloys.
  • Al-Zn-Mg-Cu alloys (belonging to the family of 7xxx alloys) are commonly used in aircraft construction, and in particular in the construction of civil aircraft wings.
  • alloy designations well known to the man of business, correspond to those of The Aluminum Association.
  • alloys 7075 and 7175 (zinc content between 5.1 and 6.1% by weight), 7050 (zinc content between 5.7 and 6.7%). , 7150 (zinc content between 5.9 and 6.9%) and 7049 (zinc content between 7.2 and 8.2%). They have a high yield strength, good toughness and good resistance to stress corrosion and exfoliating corrosion. More recently, it has been found that for certain applications, the use of an alloy with a higher zinc content may have advantages because it makes it possible to further increase the yield strength. Alloys 7349 and 7449 contain between 7.5 and 8.7% zinc. of the Wrought alloys richer in zinc have been described in the literature, but do not appear to be used in aeronautical construction.
  • the patent US5,560,789 discloses an alloy of composition Zn 10.7%, Mg 2.84%, Cu 0.92% which is processed by spinning. These alloys are not optimized specifically for a compromise static mechanical characteristics - toughness.
  • the patent US5,221,377 discloses several Al-Zn-Mg-Cu alloys with a zinc content up to 11.4%. These alloys, as will be explained below, do not meet the objectives of the present invention either.
  • the problem to which the present invention attempts to respond is therefore to propose new wrought products of high zinc content Al-Zn-Mg-Cu type alloy, greater than 8.3%, which are characterized by an improved compromise between toughness. and static mechanical characteristics (ultimate strength, yield strength), which have sufficient corrosion resistance and high elongation, and which can be industrially manufactured under conditions of reliability compatible with the high demands of the industry aeronautics.
  • the Applicant has found that the problem can be solved by adjusting the concentration of the Zn, Cu and Mg addition elements and certain impurities (especially Fe and Si) in a fine way, and possibly adding other elements.
  • a third object of the present invention is a structural element for aircraft construction which incorporates one of said products, including a structural element used in the construction of the wing boxes of civil aircraft, such as a wing extrados.
  • the figure 1 schematically shows a wing box of an airplane.
  • the landmarks are: 1, 4 extrados 2 intrados 3 spar 5 Stiffener 6 Box height 7 Width of the box
  • the figure 2 represents the mechanical resistance - damage tolerance compromise in an R p0.2 - K app diagram for the alloys of Example 3.
  • the figure 3 represents the mechanical resistance - damage tolerance compromise in an R p0.2 - K app diagram for the alloys of Example 5.
  • the K IC toughness in planar deformations was determined according to the ASTM E399 standard.
  • the K app parameter was measured according to ASTM E561 standard on CT type specimens of W width equal to 127 mm.
  • the term "spun product” includes so-called “stretched” products, i.e., products that are made by spinning followed by stretching.
  • the problem is solved by finely adjusting the contents of the alloying elements and certain impurities, and by adding a controlled concentration of certain other elements to the composition of the alloy.
  • the alloys according to the invention must contain at least 0.5% magnesium, since it is not possible to obtain satisfactory static mechanical characteristics with a lower magnesium content. According to the findings of the applicant, with a zinc content of less than 8.3%, one does not obtain a result that is better than those obtained with known alloys.
  • the zinc content is greater than 9.0%, and even more preferably greater than 9.5%. However, it is necessary to respect certain relationships between certain elements, as explained later.
  • the zinc content is between 9.0 and 11.0%. In any case, we do not want to exceed a zinc content of about 14%, because beyond this value, regardless of the magnesium and copper content, the results are not satisfactory.
  • the addition of at least 0.3% copper improves corrosion resistance. But to ensure a satisfactory dissolution, the Cu content should not exceed about 4%, and the Mg content should not exceed about 4.5%; maximum contents of 3.0% are preferred for each of these two elements.
  • the alloy must be sufficiently loaded with addition elements capable of precipitating during a maturation or a treatment of income, in order to be able to present interesting static mechanical characteristics.
  • addition elements capable of precipitating during a maturation or a treatment of income, in order to be able to present interesting static mechanical characteristics.
  • the content of these additive elements must fulfill the condition Mg + Cu> 6.4 0.4 Zn.
  • anti-recrystallizing elements More specifically, for alloys with more than 9.5% zinc, at least one element selected from the group comprising the elements Zr, Sc, Hf, La, Ti, Y, Ce, Nd, Eu, Gd, must be added. Tb, Dy, Ho, Er, Yb, Cr, Mn with, for each element present, a concentration of between 0.02 and 0.7%. It is preferable that the concentration of all the elements of said group does not exceed 1.5%.
  • zirconium with a content of between 0.03% and 0.15%, and in addition at least an element selected from the group comprising the elements Sc, Hf, La, Ti, Y, Ce, Nd, Eu, Gd, Tb, Dy, Ho, Er, Yb, with, for each element present, a concentration of between 0, 02 and 0.7%.
  • the plaintiff has found that for the said anti-recrystallizing elements, it is advantageous, irrespective of the zinc content, not to exceed the following maximum levels: Cr 0.40; Mn 0.60; Sc 0.50; Zr 0.15; Hf 0.60; Ti, 0.15; This 0.35 and preferably 0.30; Nd 0, 35 and preferably 0.30; Eu 0.35 and preferably 0.30; Gd 0.35; Tb 0.35; Ho, 0.40; Dy 0.40; Er 0.40; Yb 0.40; Y, 0.20; 0.35 and preferably 0.30.
  • the total of these elements does not exceed 1.5%.
  • Another technical characteristic is related to the need to be able to industrially produce wrought products under conditions of reliability compatible with the high requirements of the aeronautical industry, as well as under satisfactory economic conditions. It is therefore necessary to choose a chemical composition which minimizes the occurrence of cracks or cracks during the solidification of the plates or billets, said cracks or cracks being unacceptable defects leading to the scrapping of said plates or billets.
  • the Applicant has found in numerous tests that this occurrence of cracks or splits was much more likely when the 7000 alloys complete their solidification below 470 ° C.
  • Another technical feature of the invention is related to the need to minimize as much as possible the amount of insoluble precipitates after the homogenization and dissolution treatments, as this reduces the toughness; for this, we choose a content of Mg, Cu and Zn such that Mg + Cu ⁇ 7.7 - 0.4 Zn.
  • Said precipitates are typically ternary or quaternary phases Al-Zn-Mg-Cu type S, M or T.
  • the Applicant has found that the incorporation of a small amount, between 0.02 and 0.15% per element, of one or more elements selected from the group consisting of Sn, Cd, Ag, Ge, In allows to improve the response of the alloy to the treatment of income, and has beneficial effects on the mechanical strength and on the corrosion resistance of the product.
  • a content of between 0.05 and 0.10% is preferred.
  • money is the preferred element.
  • the products according to the invention are in particular rolled or spun products. They can be used advantageously for the manufacture of structural elements in aeronautical construction.
  • a preferred application of the products according to the invention is the application as a structural element in a wing box, and in particular in its upper part (extrados) which is first dimensioned in compressive strength.
  • the figure 1 schematically shows a section of the wing box of a civil aircraft.
  • a wing box typically has a length of between 10 m and 40 m and a width of between 2 m and 10 m; its height varies according to the place on the wing and is typically between 0.2 m and 2 m.
  • the box consists of the extrados (1) and the intrados (2).
  • the extrados (1) of a civil aircraft consists of a strong plate of a typical thickness during delivery between 15 mm and 60 mm, and stiffeners (5) which can be made from profiles and attached to the skin using mechanical fasteners (such as rivets or bolts) or welding techniques (such as arc welding, laser beam welding, or friction welding).
  • the extrados structure can also be obtained by assembling other aluminum alloy semi-finished products. It can also be obtained by integral machining of heavy plates or profiles, that is to say without assembly.
  • the length of the airplane wings may exceed 20 m and even 30 m, which requires the use of sheets or profiles longer than 20 m or 30 m, to minimize the assembly of the structural elements.
  • the manufacture of sheets or profiles of such a size in highly charged Al-Zn-Mg-Cu alloys requires excellent control of the casting, rolling and thermal and thermomechanical processes, and requires an adaptation of the chemical composition. according to the invention.
  • the products according to the invention can be used as structural elements in aeronautical construction.
  • a metallurgical state of T6 type for example T651
  • T7 state One can also consider the use in the T7 state.
  • Rolled, extruded or forged semi-finished products can be produced which have a very interesting compromise of properties, particularly for the aeronautical construction: a yield strength R p0.2 (L) greater than 630 MPa and even greater than 640 MPa, a toughness K IC (LT) greater than 23 MPa ⁇ m and even greater than 25 MPa ⁇ m, an elongation at break A% higher than 8% and even greater than 10%, while maintaining the resistance to exfoliating corrosion and stress corrosion at a level at least comparable to that of known Al-Zn-Mg-Cu alloys.
  • L yield strength
  • LT toughness K IC
  • the product according to the invention is particularly suitable for use as a structural element in a wing box, for example in the form of an extrados or a stiffener.
  • the advantages of the products according to the invention allow in particular their use as structural elements of very large aircraft, including civil aircraft, and especially in the form of rolled and spun products.
  • these structural elements are made from sheets with a thickness greater than 60 mm.
  • the addition of one or more anti-recrystallizing elements is particularly advantageous; such an effect is also observed in the case of heavy plates.
  • the added anti-recrystallizing element is scandium, a content of between 0.02 and 0.50% is advantageous.
  • Adding a small amount of money or some other element such as Cd, Ge, In, Sn improves income efficiency, and positive effects on the mechanical strength and stress corrosion resistance of the product.
  • the alloy A is a 7449 alloy according to the state of the art
  • the alloys B and C are alloys with a high Zn content, not respecting the technical characteristics of the invention
  • the alloy D is an alloy according to the invention. 'invention.
  • the alloy according to the invention has a better compromise static characteristics / toughness than the alloy 7449 according to the prior art (R p0.2 in tension and in higher compression and K IC similar), and that the alloys with a high zinc content which do not respect the technical characteristics of the invention are less efficient.
  • the alloy E is a 7449 alloy
  • the alloy F is an alloy according to the invention containing an addition of 0.083% Scandium.
  • Table 4 The static mechanical characteristics obtained in the T651 state are presented in Table 4 below. Toughness has been characterized using the Kahn indicator, well known to those skilled in the art and described in particular in the article by JG Kaufman and AH Knoll, "Kahn-Type Tear Tests and Crack Toughness of Aluminum Sheet", published in Materials Research & Standards, pp. 151-155, in 1964 .
  • the K app parameter was measured according to ASTM E561 standard on CT type specimens of W width equal to 127 mm.
  • the parameter K app is the stress intensity factor calculated using the maximum load measured during the test and the initial crack length (at the end of pre-cracking) in the formulas indicated by the standard. cited. These indicators are conventionally used to measure the toughness in plane stresses. The results of the tenacity measurements made during this test are shown in Table 5 below.
  • the alloy R is a 7449 alloy
  • the alloy S is an alloy according to the invention containing an addition of 0.078% of scandium.
  • the alloys G1, G2, G3 and G4 are outside the present invention, as well as the alloys B and C, described in Example 1.
  • the alloy D is an alloy according to the invention described in Example 1. All of these alloys showed satisfactory flowability during the tests, i.e. splits or cracks were not observed in the casting tests on an industrial scale.
  • the alloys G5, G6, G7, G8 are outside the present invention, and the alloy G9 is a 7060 alloy according to the state of the art; these alloys showed slits during casting tests.
  • the difficulties arising during the casting of these alloys do not necessarily make the wrought products obtained from these plates unsuitable for use, but are the cause of additional costs because the implementation (that is to say the quantity of salable metal relative to the quantity of metal fired, a parameter which is directly related to the quantity of scraped plates) will be greater than for the alloys corresponding to the preferred domain of the invention.
  • the propensity of these alloys for the formation of slits during their solidification makes it very difficult to make the casting process reliable in the context of a quality assurance program by statistical process control.
  • Rolling plates were developed by a process similar to that described in Example 1.
  • the chemical composition is given in Table 10.
  • it was prepared by hot rolling. 25 mm thick sheets. They were dissolved for 2 hours at a temperature of between 472 and 480 ° C. (these temperatures are determined by preliminary calorimetry tests on the raw rolling sheets, a procedure that is conventional for those skilled in the art), quenched by spraying. and tractionned with a permanent elongation of between 1.5 and 2%. Then the sheets were subjected to a tempering treatment at a temperature of 135 ° C.
  • Example 3 we have represented the mechanical resistance - damage tolerance compromise in an R p0.2 - K app diagram. This diagram is provided at figure 3 for the alloys of Example 5. With an equal zinc content, and an equal scandium content, the sheet K with a lower Mg / Cu ratio shows significantly better toughness values than the N sheet.
  • Spinning billets 291 mm in diameter with an alloy according to the invention were prepared by vertical casting, the composition of which is given in Table 12.
  • Table 12 Alloy Zn mg Cu Cr mn Yes Fe Zr Ti Mg / Cu T 9.43 1.96 1.67 - 0.01 0.05 0.07 0.12 0.03 1.17
  • the geometry of the profiles comprises a sole (thickness 15 mm, width 152 mm), a rib (thickness 15 mm, height 38 mm) and a reinforcement (thickness 23 mm, width 76 mm).
EP03740568A 2002-04-05 2003-04-04 Produits en alliages al-zn-mg-cu Revoked EP1492895B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0204257A FR2838136B1 (fr) 2002-04-05 2002-04-05 PRODUITS EN ALLIAGE A1-Zn-Mg-Cu A COMPROMIS CARACTERISTIQUES STATISTIQUES/TOLERANCE AUX DOMMAGES AMELIORE
FR0204257 2002-04-05
PCT/FR2003/001062 WO2003085145A2 (fr) 2002-04-05 2003-04-04 Produits en alliages al-zn-mg- cu

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Publication Number Publication Date
EP1492895A2 EP1492895A2 (fr) 2005-01-05
EP1492895B1 true EP1492895B1 (fr) 2009-12-16

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US (1) US7550110B2 (ja)
EP (1) EP1492895B1 (ja)
JP (1) JP4535731B2 (ja)
AT (1) ATE452216T1 (ja)
AU (1) AU2003260001A1 (ja)
DE (2) DE60330547D1 (ja)
ES (1) ES2338314T3 (ja)
FR (1) FR2838136B1 (ja)
WO (1) WO2003085145A2 (ja)

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DE60330547D1 (de) 2010-01-28
AU2003260001A1 (en) 2003-10-20
JP4535731B2 (ja) 2010-09-01
ES2338314T3 (es) 2010-05-06
FR2838136A1 (fr) 2003-10-10
WO2003085145A3 (fr) 2004-04-01
DE03740568T1 (de) 2005-07-14
ATE452216T1 (de) 2010-01-15
US20030219353A1 (en) 2003-11-27
WO2003085145A2 (fr) 2003-10-16
US7550110B2 (en) 2009-06-23
EP1492895A2 (fr) 2005-01-05
FR2838136B1 (fr) 2005-01-28
JP2005528521A (ja) 2005-09-22

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