EP1683882B2 - Alliage d'Aluminium avec sensitivité à la trempe réduite et procédé de fabrication d'un produit demi-final lors de cet alliage - Google Patents

Alliage d'Aluminium avec sensitivité à la trempe réduite et procédé de fabrication d'un produit demi-final lors de cet alliage Download PDF

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EP1683882B2
EP1683882B2 EP05111026A EP05111026A EP1683882B2 EP 1683882 B2 EP1683882 B2 EP 1683882B2 EP 05111026 A EP05111026 A EP 05111026A EP 05111026 A EP05111026 A EP 05111026A EP 1683882 B2 EP1683882 B2 EP 1683882B2
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maximum
finished product
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EP1683882A1 (fr
EP1683882B1 (fr
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Matthias Dr.-Ing. Hilpert
Gregor Dr. Terlinde
Gernot Dr. Fischer
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Otto Fuchs KG
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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
    • C22F1/053—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals

Definitions

  • the invention relates to a quench-resistant aluminum alloy for the production of high-strength, low-intrinsic forgings and high-strength extruded and rolled products. Furthermore, the invention relates to a method for producing a semi-finished product from such an aluminum alloy.
  • high-strength aluminum alloys are needed for the production of, in particular, load-bearing fuselage, wing and chassis parts, which have high strength both under static and dynamic load.
  • the required strength properties can be achieved in the abovementioned semi-finished products by using alloys of the 7000 group (7xxx alloy) in accordance with the classification of aluminum alloys by the Aluminum Association (AA).
  • die forgings for high-stress aerospace parts are made of the AA 7075, AA 7175, AA 7475 and more preferably AA 7049 and AA 7050 alloys in the Americas and the AA 7010, AA 7049A and AA 7050A alloys used in the European area.
  • WO 02/052053 A1 is a high strength aluminum alloy of the aforementioned type with a higher zinc content compared to previous alloys of the same type coupled with a reduced copper and magnesium content.
  • the copper and magnesium content in this prior art alloy together is less than 3.5%.
  • the copper content itself is given as 1.2-2.2% by weight, preferably 1.6-1.2% by weight.
  • this prior art alloy necessarily contains one or more elements from the group of zirconium, scandium and hafnium with maximum proportions of 0.4% by weight zirconium, 0.4% by weight scandium and 0, 3% by weight hafnium.
  • the semi-finished products produced from one of the abovementioned alloys that is to say for example the forgings, the extruded profiles or the rolled plates, obtain the desired strength
  • the semi-finished products are subjected to a special heat treatment. This involves quenching of solution annealing temperature, usually associated with subsequent cold working at average thicknesses greater than 50 mm.
  • Cold forming serves to reduce the stresses induced during quenching.
  • the step of cold forming can be done by a cold heading or by stretching the semi-finished product typically by 1-3%.
  • the semi-finished products produced should be as low in natural stress as possible in order to minimize undesirable distortion during further processing of the semi-finished products.
  • the semi-finished products and, accordingly, also the prefabricated parts made therefrom should be low-stress, in order to give the designer the opportunity to utilize the entire material potential.
  • the process steps to be used for producing parts for aerospace engineering and also the maximum thickness of the semi-finished products used for the production of the parts are standardized or prescribed.
  • the maximum permissible thickness is 200 mm and assumes that after quenching the semi-finished product is necessarily subjected to a cold-forming step for the abovementioned reasons.
  • cold forming is relatively easy to achieve due to the generally simple geometry of stretching in the longitudinal direction.
  • larger and especially thicker forgings are needed.
  • US 4 629 517 A discloses an aluminum product having good strength properties and good corrosion resistance when in the T76 state.
  • the aluminum product consists of an AA 7xxx alloy containing 0.08 wt% Si, 0.29 wt% Fe, 0.20 wt% Cu, 0.03 wt% Mn, 2.5 Wt% Mg, 0.03 wt% Cr, 7.1 wt% Zn, 0.12 wt% Zr and 0.06 wt% Ti.
  • the method described in this document is only suitable for producing aluminum products having a thickness of a few millimeters.
  • the alloy described in this document is not suitable for the production of semi-finished products with medium and larger thicknesses and the required strengths.
  • the invention has the object, a method for producing a semifinished product with to suggest the desired properties of this alloy.
  • the alloy-related object is achieved by a high-strength, quench-resistant aluminum alloy having the features of claim 1.
  • the method-related object is achieved by a method according to claim 9 or claim 12.
  • Medium-sized semi-finished products have a thickness of between 50 and 180 mm.
  • Semi-finished products with a greater thickness have a coating thickness of> 180 mm.
  • the quenching-resistant alloy according to the invention can also be used to produce semi-finished products in a thickness of more than 200 mm, in particular 250 mm and more, with the desired high static and dynamic strength properties while at the same time having good fracture toughness and good stress-crack corrosion behavior. Only at these larger thicknesses a cold forming step is advantageously carried out to reduce the quench-induced residual stresses.
  • semi-finished products produced for average thicknesses of the alloy may be mildly mild after solution annealing.
  • B. can be cooled in a glycol-water mixture without the very good material properties are significantly impaired after a subsequent thermal aging.
  • the step of cold forming is omitted for medium thicknesses, since the residual stresses induced by the mild cooling are not critically low. Therefore, it is possible with this alloy to produce semi-finished products in the middle thickness range in a simpler and more cost-effective manner, namely without an otherwise necessary cold forming step.
  • the above-described advantageous properties of the alloy can also be utilized to simplify the manufacturing process of a part, for the manufacture of which a semifinished product of greater initial thickness is required and which has an average thickness after being machined.
  • a semifinished product of greater thickness is pre-machined after the step of hot forming.
  • the preprocessing is designed so that the semifinished product to be quenched in the course of the heat treatment undergoes such a thickness reduction, which is anyway necessary for the production of the finished part, that the semi-finished product is subjected to a heat treatment with mild quenching (glycol / water quenching) without carrying out a cold forming step otherwise necessary for larger thicknesses. Mixture) can be subjected.
  • the above-mentioned properties of the semifinished product produced from this alloy are unexpected since, contrary to the specifications resulting from the prior art, the copper content is significantly lower than was the case with previously known high-strength aluminum alloys. According to a preferred embodiment, the copper content is only 0.8-1.1 wt%. Thus, the copper content is only about 50% of the preferred copper content of the WO 02/052053 A1 known aluminum alloys. That nevertheless very high strength values are achieved, is surprising. These properties are believed to be due to the balanced composition of the alloy constituents, which includes the relatively high levels of zinc and the magnesium content adjusted to it. The balanced composition of the alloying elements permitted within narrow limits provides that the sum of the elements magnesium, copper and zinc is at least 9% by weight.
  • the alloy has a zinc: magnesium ratio of between 4.4 and 5.3. It has been found that the desired strength properties can only be achieved if the elements magnesium, copper and zinc in the sum more than 9 wt .-% and the zinc: magnesium ratio. These characteristics of the alloy are a measure of how the products made with the alloy have the desired strength properties. This regulation also determines the hardenability of the semi-finished products produced with the alloy.
  • silver addition may be advantageous.
  • the content will be limited to 0.2-0.7%, in particular 0.20-0.40% by weight.
  • the manganese content of the alloy was limited to a maximum of 0.5% by weight.
  • the hardenability of an Al-Zn-Cu-Mg alloy decreases with increasing manganese content. For this reason, the manganese content is limited.
  • zirconium additive This is according to a preferred embodiment, 0.14 - 0.20 wt .-%.
  • Zirconium also precipitates out of the microstructure during the homogenization of the continuous casting ingots in the form of zirconium aluminides. These aluminides are generally more finely dispersed than the manganese aluminides. Therefore, they are especially helpful in terms of recrystallization control.
  • the zirconium aluminides formed are not coarsened by the intended heat treatment and are stable in the selected temperature ranges, unlike manganese aluminides. For this reason, zirconium is a necessary component of the alloy.
  • the titanium contained in the alloy is primarily used for grain refining during continuous casting. Preference is given to adding from 0.03 to 0.1% by weight of titanium, in particular from 0.03 to 0.06% by weight, of titanium.
  • the alloy may contain 0.001-0.03 wt% boron. Furthermore, the alloy can max. 0.2% by weight of cerium and max. 0.30 wt .-% scandium.
  • the desired properties are achieved if the specified alloying constituents are used proportionally in the specified range. With an alloy in which one or more alloying constituents have a content which is outside the stated range, semi-finished products can no longer be produced with the required properties.
  • thermosetting of the quenched semifinished product takes place in two stages, wherein in the first stage, the semi-finished product is heated to a temperature of more than 100 ° C and held for more than eight hours at this temperature and in the second stage heated to more than 130 ° C and heated for more than five hours. These two steps can be carried out immediately after each other. Without prejudice to the desired properties of the semifinished product, the semifinished product treated with the first stage can also be cooled and the second stage of the thermosetting can be carried out at a later time.
  • the two alloys Z1, Z2 had the following composition: Si Fe Cu Mn mg Cr Zn Ti Zr Ti + Zr Alloy Z1 0.05 0.05 0.95 0.39 1.70 0,002 8.35 0,035 0.12 0,155 Alloy Z2 0.04 0.07 0.90 0,004 1.65 0.001 8.50 0,025 0.12 0.145
  • Alloys Z1, Z2 were cast on an industrial scale to 370 mm diameter continuous casting blocks.
  • the continuous casting blocks were homogenized to compensate for the crystallization induced crystallization.
  • the blocks were homogenized in two stages in a temperature range of 465 ° C - 485 ° C and cooled.
  • the homogenized blocks were preheated to 370 ° C and remolded into open-die forgings 250 mm thick and 500 mm wide.
  • the forgings made of Alloy Z1 and Z2 were solution-annealed for at least 4 hours at 485 ° C, quenched in water at room temperature and then cured between 100 ° C and 160 ° C warm, wherein the hot curing has been carried out in two stages.
  • the semi-finished product was heated to more than 100 ° C and held at this temperature for more than eight hours.
  • the second stage carried out after the first stage was carried out at a temperature of more than 130 ° C for more than five hours.
  • the K lC values are given below: alloy test direction location K IC (MPa - ⁇ m) R p0.2 (MPa) Z 1 LT edge 30.5 529 LT core 32.9 504 TL edge 23.1 516 TL core 20.4 502 Z 2 LT edge 30.3 514 LT core 35.9 520 TL edge 23.6 514 TL core 21.8 508
  • alloy Z1 alloy load direction Rp02 (MPa)
  • R m (MPa) A 5 (%) Z 1 L 504 523 11.2 LT 502 533 5.2 ST 498 522 8.0
  • the A 5 values are highest for the L direction and reach at least 6% elongation at break (A 5 ) for the two transverse directions.
  • the strength drop can be reduced.
  • W 50 mm
  • the fracture toughness K lc in the test specimens LT and TL was determined according to ASTM-E 399.
  • the K lC values are given in the following table: alloy test direction location K lC (MPa ⁇ m) R p0.2 ( Mpa ) Z 1 LT edge 30.5 529 LT core 32.9 504 TL edge 23.1 516 TL core 20.4 502 Z 1 + cold diving LT edge 38.9 485 LT core 42.2 448 TL edge 23.9 474 TL core 21.9 468
  • open-die forgings with a thickness of 150 mm and a width of 500 mm were produced from Alloy Z1 and, according to the example described above, after solution heat treatment in water or in a water-glycol mixture with about 20% or approx. 40% quenched and warmed up as previously described. A forging was additionally cold-crushed after quenching in water. Tensile specimens taken from the forgings in the "long" (L), "long-transverse” (LT) and “short-transverse” (ST) directions, the influence of different cooling media was shown.
  • Alloy Z1 for a thickness of 150 mm for different cooling treatments are shown below: quenching load direction Rp02 (MPa) R m (MPa) A 5 (%) Water (RT) L 551 573 10, 3 LT 515 544 7.5 ST 505 549 8.0 Water (RT) + cold diving L 491 537 12.8 LT 465 520 8.7 ST 430 513 8.5 Water / glycol (16-20%) L 545 566 12.5 LT 520 547 7.2 ST 512 548 8.3 Water / glycol (38-40%) L 503 529 12.2 LT 493 525 5.0 ST 487 526 5.6
  • the fracture toughness K lc in the test specimens LT and TL was determined according to ASTM-E 399.
  • the K lC values are shown in the following table: quenching test direction K lC (MPa ⁇ m) Rp02 (MPa) Water (RT) LT 36.8 551 TL 23.8 515 Water (RT) + cold diving LT 39.1 491 TL 24.1 465 Water / glycol (16-20%) LT 28.2 545 TL 20.7 520 Water glycol (38-40%) LT 35.4 503 TL 18.5 493
  • the alloy Z1 was cast analogously to the first example and produced blocks for extrusion in yet another example.
  • the homogenized blocks were preheated to over 370 ° C and extruded into extruded profiles having a rectangular cross section of 40 mm thickness and a width of 100 mm.
  • the profiles were then solution-annealed for at least 4 hours at 485 ° C., quenched in water at room temperature and then heated between 100 ° C. and 160 ° C. in two stages (first stage:> 100 ° C.,> 8 h, second stage:> 130 ° C,> 5h) cured.
  • the A 5 values are highest for the L direction and reach at least 7% elongation at break (A 5 ) for the two transverse directions.
  • FIG. 1 is a graph showing the strength behavior of various AA 7xxx alloys as a function of the average cooling rate during quenching from the solution annealing temperature.
  • FIG. It is clearly recognizable in this presentation that the loss of strength when using the claimed aluminum alloy is considerably lower even at low cooling rates than in the case of the comparative alloys AA 7075, AA 7010 and AA 7050.
  • the strength values of the products / semi-finished products produced with the claimed alloy as determined in the context of the description of the invention are considerably improved, in particular with regard to the stress-crack corrosion resistance compared to products of prior art alloys, which is a result which could not be foreseen in the form shown.
  • the results presented are also interesting in that the strength values described can be represented in particular in the case of hot curing carried out only in two stages.

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Claims (13)

  1. Alliage d'aluminium à sensibilité réduite à la trempe destiné à fabriquer des pièces forgées à haute résistance et à faible contrainte résiduelle ainsi que des produits filés et laminés à haute résistance constitué de :
    - 7,0 - 10,5 % en poids de zinc,
    - 1,0 - 2,5 % en poids de magnésium,
    - 0,1-1,15% en poids de cuivre
    - 0,06 - 0,25 % en poids de zircon,
    - 0,02-0,15% en poids de titane,
    - maximum 0,5 % en poids de manganèse,
    - maximum 0,6 % en poids d'argent,
    - maximum 0,10 % en poids de silicium,
    - maximum 0,10 % en poids de fer,
    - maximum 0,04 % en poids de chrome,
    - ainsi qu'à titre facultatif un ou plusieurs éléments du groupe hafnium, scandium, strontium et/ou vanadium avec une teneur totale de 1,0 % en poids au maximum,
    - ainsi qu'à titre facultatif 0,001 - 0,03 % en poids de bore,
    - ainsi qu'à titre facultatif maximum 0,2 % en poids de cérium et maximum 0,30 % en poids scandium,
    - ainsi qu'à titre facultatif 0,2 % en poids de cérium au maximum,
    - en plus d'impuretés diverses avec une teneur de 0,05 % en poids au maximum par élément et une teneur totale de 0,15 % en poids au maximum,
    - le reste : de l'aluminium,
    - la somme des éléments d'alliage de zinc, de magnésium et de cuivre s'élevant à au moins 9 % en poids et
    - le rapport zinc : magnésium de l'alliage se situant entre 4,4 et 5,3.
  2. Alliage d'aluminium selon la revendication 1 caractérisé en ce que l'alliage contient 1,6 - 1,8 % en poids de magnésium et 0,8 - 1,1 % en poids de cuivre.
  3. Alliage d'aluminium selon la revendication 1 caractérisé en ce que l'alliage d'aluminium contient 0,8 -1,1 % en poids de cuivre et 0,3 - 0,5 % en poids de manganèse.
  4. Alliage d'aluminium selon la revendication 1 caractérisé en ce que l'alliage d'aluminium contient 0,8 - 1,1 % en poids de cuivre et au maximum 0,03 % en poids de manganèse.
  5. Alliage d'aluminium selon la revendication 1 caractérisé en ce que l'alliage d'aluminium contient 0,2 - 0,3 % en poids de cuivre et 0,25 - 0,40 % en poids d'argent.
  6. Alliage d'aluminium selon l'une des revendications 1 à 5 caractérisé en ce que l'alliage d'aluminium contient 0,10 - 0,15 % en poids de titane.
  7. Alliage d'aluminium selon l'une des revendications 1 à 6 caractérisé en ce que l'alliage contient au maximum 0,30 % en poids de scandium et au maximum 0,2 % en poids de vanadium, de hafnium ou de cérium.
  8. Alliage d'aluminium selon l'une des revendications 1 à 7 caractérisé en ce que la teneur en fer et en silicium représente respectivement au maximum 0,08 % en poids.
  9. Procédé pour fabriquer à partir d'un alliage d'aluminium selon l'une des revendications 1 à 8, un demi-produit à haute résistance, à faible contrainte résiduelle, selon les étapes suivantes :
    - Formage à chaud des barres homogénéisées par forgeage, filage et/ou laminage dans une plage de températures de 350 - 440 °C ;
    - Mise en solution du demi-produit formé à chaud à des températures suffisamment élevées afin de mettre en solution pour une répartition homogène dans la structure des éléments d'alliage indispensables au durcissement structural, de préférence à 465 - 500 °C ;
    - Trempe des demi-produits, préalablement soumis au recuit de mise en solution, dans l'eau, dans un mélange eau-glycol ou dans un mélange salin à des températures entre 100 °C et 170°C;
    - Formage à froid du demi-produit trempé afin de réduire les contraintes résiduelles survenues lors de la trempe dans un médium de refroidissement ; et
    - Revenu en un ou plusieurs paliers du demi-produit préalablement trempé, les taux d'échauffement, les temps de séjour et les températures étant ajustés en vue d'une optimisation des propriétés du matériau.
  10. Procédé selon la revendication 9 caractérisé en ce que l'étape de formage à froid est réalisée par refoulement ou étirage du demi-produit.
  11. Procédé selon la revendication 9 ou 10 caractérisé en ce que le taux de formage à froid représente 1 - 5 %.
  12. Procédé pour fabriquer à partir d'un alliage d'aluminium selon l'une des revendications 1 à 8, un demi-produit à haute résistance, à faible contrainte résiduelle, d'une épaisseur de traitement de 50 - 180 mm, selon les étapes suivantes :
    - Formage à chaud des barres homogénéisées par forgeage, filage et/ou laminage dans une plage de températures de 350 - 440 °C ;
    - Mise en solution du demi-produit formé à chaud à des températures suffisamment élevées afin de mettre en solution pour une répartition homogène dans la structure des éléments d'alliage indispensables au durcissement structural, de préférence à 465 - 500 °C ;
    - Trempe des demi-produits, préalablement soumis au recuit de mise en solution, dans l'eau, dans un mélange eau-glycol ou dans un mélange salin à des températures entre 100 °C et 170°C;
    - Revenu en un ou plusieurs paliers du demi-produit préalablement trempé, les taux d'échauffement, les temps de séjour et les températures étant ajustés en vue d'une optimisation des propriétés du matériau.
  13. Procédé selon la revendication 12 caractérisé en ce qu'après l'étape de formage à chaud, on dispose d'un demi-produit d'une épaisseur de traitement supérieure à 180 mm, qui, avant le traitement thermique à venir, sera d'abord usiné par enlèvement de copeaux, afin de réduire par l'enlèvement des copeaux l'épaisseur du demi-produit de telle sorte que ce demi-produit préalablement usiné présente une épaisseur de traitement de 50 - 180 mm et que le traitement thermique à suivre soit réalisé conformément aux exigences applicables aux demi-produits d'une épaisseur de traitement de 50-180 mm.
EP05111026A 2005-01-19 2005-11-21 Alliage d'Aluminium avec sensitivité à la trempe réduite et procédé de fabrication d'un produit demi-final lors de cet alliage Active EP1683882B2 (fr)

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ES2292075T5 (es) 2005-01-19 2010-12-17 Otto Fuchs Kg Aleacion de aluminio no sensible al enfriamiento brusco, asi como procedimiento para fabricar un producto semiacabado a partir de esta aleacion.
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CN101818290A (zh) * 2010-05-28 2010-09-01 中南大学 一种同时添加Ag、Ge的低淬火敏感性铝合金
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ES2292075T5 (es) 2010-12-17
US20140099230A1 (en) 2014-04-10
US20120202086A1 (en) 2012-08-09
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US10301710B2 (en) 2019-05-28
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