US20050034794A1 - High strength Al-Zn alloy and method for producing such an alloy product - Google Patents

High strength Al-Zn alloy and method for producing such an alloy product Download PDF

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US20050034794A1
US20050034794A1 US10/819,130 US81913004A US2005034794A1 US 20050034794 A1 US20050034794 A1 US 20050034794A1 US 81913004 A US81913004 A US 81913004A US 2005034794 A1 US2005034794 A1 US 2005034794A1
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alloy
product
alloy according
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weight
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Rinze Benedictus
Christian Keidel
Alfred Heinz
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Novelis Koblenz GmbH
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Corus Aluminium Walzprodukte GmbH
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Priority to US12/547,466 priority patent/US20090320969A1/en
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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 a wrought high strength Al—Zn alloy product with an improved combination of corrosion resistance and toughness, a method for producing a wrought high strength Al—Zn alloy product with an improved combination of corrosion resistance and toughness and a plate product of such alloy, optionally produced in accordance with the method. More specifically, the present invention relates to a wrought high strength Al—Zn alloy designated by the 7000-series of the international nomenclature of the Aluminium Association for structural aeronautical applications. Even more specifically, the present invention relates to a new chemistry window for an Al—Zn alloy product having improved combinations of strength, toughness and corrosion resistance, which does not need specific ageing or temper treatments.
  • Aluminium alloys AA7050 and AA7150 exhibit high strength in T6-type tempers, see e.g. U.S. Pat. No. 6,315,842. Also precipitation-hardened AA7 ⁇ 75, AA7x55 alloy products exhibit high strength values in the T6 temper.
  • the T6 temper is known to enhance the strength of the alloy, wherein the aforementioned AA7x50, AA7x75 and AA7x55 alloy products which contain high amounts of zinc, copper and magnesium are known for their high strength-to-weight ratios and, therefore, find application in particular in the aircraft industry.
  • these applications result in exposure to a wide variety of climatic conditions necessitating careful control of working and ageing conditions to provide adequate strength and resistance to corrosion, including both stress corrosion and exfoliation.
  • T74 temper is a limited over-aged condition, between T73 and T76, in order to obtain an acceptable level of tensile strength, stress corrosion resistance, exfoliation corrosion resistance and fracture toughness.
  • T74 temper is performed by over-ageing the aluminium alloy product at temperatures of 121° C. for 6 to 24 hours and 171° C. for about 14 hours.
  • EP-0377779 discloses an improved process for producing a 7055 alloy for sheet or thin plate applications in the field of aerospace such as upper-wing members with high toughness and good corrosion properties which comprises the steps of working a body having a composition consisting of, in wt. %:
  • U.S. Pat. No. 5,312,498 discloses another method for producing an aluminium-based alloy product having improved exfoliation resistance and fracture toughness with balanced zinc, copper and magnesium levels such that there is no excess of copper and magnesium.
  • the method of producing the aluminium-based alloy product utilizes either a one- or two-step ageing process in conjunction with the stochiometric balancing of copper, magnesium and zinc.
  • a two-step ageing sequence is disclosed wherein the alloy is first aged at approx. 121° C. for about 9 hours followed by a second ageing step at about 157° C. for about 10 to 16 hours followed by air-cooling.
  • Such ageing method is directed to thin plate or sheet products which are used for lower-wing skin applications or fuselage skin.
  • U.S. Pat. No. 4,954,188 discloses a method for providing a high strength aluminium alloy characterised by improved resistance to exfoliation using an alloy consisting of the following alloying elements, in wt. %:
  • U.S. Pat. No. 5,221,377 therefore discloses an alloy product consisting essentially of about 7.6 to 8.4 wt. % Zn, about 1.8 to 2.2 wt. % Mg and about 2.0 to 2.6 wt. % Cu. Such alloy product exhibits a yield strength which is about 10% greater than its 7x50-T6 counterpart with good toughness and corrosion resistance. The yield strength was reported to be over 579 MPa with an exfoliation resistance (EXCO) level of “EC” or better.
  • EXCO exfoliation resistance
  • U.S. Pat. No. 5,496,426 discloses an alloy as disclosed in U.S. Pat. No. 5,221,377 and a process including hot rolling, annealing and cold rolling within a preferred cold reduction range of 20% to 70% which, in turn, is preferably followed by controlled annealing thereby displaying characteristics which are better than AA7075-T6 characteristics. While the AA7075-T6 failed the stress corrosion resistance test (SCC resistance 40 days in the 35% NaCl alternate immersion test) at 138 MPa the disclosed processed alloy had a SCC resistance of 241 MPa.
  • U.S. Pat. No. 5,108,520 and U.S. Pat. No. 4,477,292 disclose an ageing process for solution-heat-treated, precipitation hardening metal alloy including three steps of ageing, comprising (1) ageing the alloy at one or more temperatures substantially above room temperature but below 163° C. to substantially below peak yield strength, (2) subsequently ageing the alloy at one or more temperatures at about 190° C. for increasing the resistance of the alloy to corrosion and thereafter, (3) ageing the alloy at one or more temperatures substantially above room temperature but below about 163° C. for increasing yield strength.
  • the resultant product displayed good strength properties and a good corrosion performance.
  • the three step ageing procedure is cumbersome and difficult to perform so that the costs for producing such alloy increase.
  • the present invention has a number of preferred objects.
  • alloy designations and temper designations refer to the Aluminum Association designations in Aluminum Standards and Data and the Registration Records, all published by the US Aluminum Association. All percentages are in weight percents, unless otherwise indicated.
  • Such chemistry window for an AA7000-series alloy exhibits excellent properties when produced to thin plate products which is preferably useable in aerospace upper-wing applications.
  • all percentages are weight percents unless otherwise indicated.
  • the above defined chemistry has properties which are comparable or better than existing alloys of the AA7x50 or AA7x55 series in the T77-temper, without using the above described cumbersome and complicated T77 ageing cycles.
  • the chemistry leads to an aluminium product which is not only superior with regard to the question of costs but also simpler to produce since less processing steps are necessary. Additionally, the chemistry allows new manufacturing techniques like age creep forming which is not feasible when a T77-temper alloy is applied. Even better, the chemistry as defined above can also be aged to the T77-temper wherein the corrosion resistance further improves as compared to the two-step ageing procedure which is described hereinbelow, wherein especially the exfoliation corrosion performance is enhanced.
  • a preferred amount of magnesium is in a range of 0.2[Cu]+1.3 ⁇ [Mg] ⁇ 0.1[Cu]+2.15, most preferably in a range of 0.2[Cu]+1.4 ⁇ [Mg] ⁇ 0.1[Cu]+1.9.
  • Copper is in a range of about 1.5 to 2.1, more preferably in a range of 1.5 to less than 2.0. The balance of magnesium and copper is important for the inventive chemistry.
  • Copper and magnesium are important elements for adding strength to the alloy. Too low amounts of magnesium and copper result in a decrease of strength while too high amounts of magnesium and copper result in a lower corrosion performance and problems with the weldability of the alloy product. Prior art techniques used special ageing procedures to ameliorate the strength and low amounts of magnesium and copper are used in order to achieve a good corrosion performance. In order to achieve a compromise in strength, toughness and corrosion performance copper and magnesium amounts (in wt. %) of between about 1.5 and 2.3 have been found to give a good balance for thick alloy products. However, the corrosion performance is the vital parameter for thin alloy products so that less amounts of copper and magnesium must be used, thereby resulting in a lower strength. Throughout the claimed chemistry of the present invention it is now possible to achieve strength levels in the region of a T6-temper alloy while maintaining corrosion performance characteristics similar to those of T74-temper alloys.
  • the improved corrosion resistance of the alloy according to the invention has exfoliation resistance properties (“EXCO”) of EB or better, preferably EA or better.
  • exfoliation properties are measured in accordance with the standards for resistance to stress corrosion cracking (“SCC”) and exfoliation resistance (“EXCO”) currently required for AA7075, AA7050 and AA7150-products aged to the T73, T74 and T76, along with typical performance of T6, tempers.
  • SCC stress corrosion cracking
  • EXCO exfoliation resistance
  • a given test specimen is subjected to predefined test conditions. Bar-shaped specimens are exposed to cycles of immersing in a 3.5% NaCl aqueous solution for 10 minutes, followed by 50 minutes of air drying while being pulled from both ends under a constant strain (stress level). Such testing is usually carried out for a minimum of 20 days (or for less time should the specimen fail or crack before 20 days have passed). This test is the ASTM standard G47 (G47-98) test.
  • Another preferred SCC-test conducted in accordance with ASTM standard G47, (G38-73) is used for extruded alloy products that include thin plate products.
  • This test consists of compressing the opposite ends of a C-shaped ring using constant strain levels and alternate immersion conditions substantially similar to those as described above. While an M7075, M7050 or M7150-T6 tempered alloy fails the SCC test in less than 20 days and while the exfoliation properties are EC or ED, the corrosion resistance performance increases with tempers T76-, T74-, T73.
  • the exfoliation properties of T73 are EA or better. Specific examples are described hereinbelow.
  • the inventive alloy has a chemistry with a preferred amount of magnesium and copper of about 1.93 when the amount (in wt. %) of zinc is about 8.1.
  • the amount (in wt. %) of zinc is in a range of 6.1 to 8.3, more preferably in a range of 6.1 to 7.0 if manganese is lower than 0.05, and preferably lower than 0.02.
  • the amount of manganese (in wt. %) is preferably in a range of about 0.06 to 0.12 when the amount of zinc is above 7.6.
  • Manganese contributes to or aids in grain size control during operations that can cause the alloy microstructure to recrystallize.
  • the preferred levels of manganese are lower than in conventional AA7000-series alloys but may be raised when zinc is raised.
  • the amount of the additional alloying elements Ce and/or Sc is smaller than 0.20, preferably in a range of 0.05 to 0.15, most preferably around 0.10.
  • a preferred method for producing a wrought high strength Al—Zn alloy product with an improved combination of corrosion resistance and toughness comprises the steps of
  • the properties of the invention may be further achieved throughout a preferred method which includes artificially ageing the worked and solution heat-treated product, wherein the ageing step comprises a first heat treatment at a temperature in a range of 105° C. to 135° C., preferably around 120° C. for 2 to 20 hours, preferably around 8 hours, and a second heat treatment at a higher temperature than 135° C. but below 210° C., preferably around 155° C. for 4 to 12 hours, preferably 8 to 10 hours.
  • a corrosion performance is achieved which is similar to the corrosion performance of a T76-temper alloy.
  • the ageing step comprises a third heat treatment at a temperature in a range of 105° C. to 135° C. for more than 20 hours and less than 30 hours.
  • This T77-temper ageing procedure is known and even increases the performance characteristics as compared to the two-step ageing procedure.
  • the two-step ageing procedure results in thin aluminium alloy products which are partially comparable and partially better than T77-temper products.
  • Such plate product of high strength Al—Zn alloy may be obtained by an alloy having a composition as described above or being produced in accordance with a method as described above.
  • Such plate product is preferably useable as thin aircraft member, more preferably as an elongated structural shape member. Even more preferred is a plate product for use as an upper-wing member, preferably a thin skin member of an upper-wing or of a stringer of an aircraft.
  • Tests were performed comparing the performance of the alloy according to the present invention and AA7150-T77 alloys. It has been found that the examples of the alloy of the present invention show an improvement over conventional AA7150-T77-temper alloys.
  • Tensile yield strength was measured according to EN 10.002
  • exfoliation resistance properties (“EXCO”) were measured according to ASTM G-34-97
  • stress corrosion cracking (“SCC”) was measured according to ASTM G-47-98
  • all in ST-direction was measured according to ASTM E-399
  • the compression yield strength (“CYS”) was measured according to ASTM E-9.
  • alloys 1, 2 and 4 show better strength/toughness combinations. Alloys 2, 3 and 4 all have an acceptable EXCO performance wherein alloys 2, 3 and 4 have a significant higher compression yield strength than alloy No. 1 (M7050-alloy). Alloys 2 and 4 exhibit a property balance that makes them very suitable for upper-wing applications in aerospace thereby showing a balance of properties which is better than those of conventional 7150-T77 alloys. However, it is still possible to use a T77-temper for the inventive alloys as shown in Table 3. TABLE 3 Alloys 2 and 4 tempered according to T77 temper conditions, overview of strength, toughness and corrosion performance.
  • alloy 4-samples were prepared according to the procedure described in ASTM G-47-98 (standard test methods for determining susceptibility to stress corrosion cracking of AA7000-series aluminium alloy products) and exposed to the corrosive atmosphere according to ASTM G-44-94 (alternate immersion in accordance with the standard practice for evaluating stress corrosion cracking resistance of metals and alloys by alternate immersion in 3.5% NaCl solution).
  • Strength and toughness properties were measured after pre-heating the cast alloys for 6 hours at 410° C. and then hot rolling the alloys to a gauge of 28 mm. Thereafter, solution heat treating was applied at 475° C. and water quenching. Ageing was done for 8 hours at 120° C. and 8 to 10 hours at 155° C. (T79-T76-temper). The results are shown in Table 6. TABLE 6 Overview of strength and toughness of 11 alloys according to Table 5 in the identified directions.
  • alloys 3 to 8 and 11 displayed good toughness properties
  • alloys 1 to 5 and 9 and 10 displayed good strength properties.
  • alloys 3, 4 and 5 show a good balance of strength and toughness so that it is clear to have a copper content of above 1.3 and a magnesium content of above 1.6 (in wt. %) when zinc is present in an amount of 8.1. Such amounts are lower limits for the copper and magnesium windows.
  • Table 6 the toughness will drop to un-acceptable low-levels when copper and magnesium levels are too high (alloys 1, 2, 9 and 10).
  • AA7055-T77 alloys are preferred instead of AA7150-T77 alloys as an alloy for upper wing applications.
  • the present invention therefore discloses optimised copper and magnesium windows which show properties equal or better to conventional AA7055-T77 alloys.
  • Alloys 1 and 2 were tested with regard to their strength properties. These properties are shown in Table 10. Alloy 2 has been tempered in accordance with two temper conditions (T79-T76 and T77). Reference alloy AA7055 has been measured in T77 temper (M-Ref) while the technical data of an AA7055 reference alloy in a T77 temper are given as well (as identified by Ref). TABLE 10 Overview of strength of the two inventive alloys of Table 9, alloy No. 2 in two temper conditions, reference alloy (AA7055) measured (M-Ref) and tech sheet (Ref).
  • the inventive alloy has similar tensile properties as a conventional AA7055-T77 alloy. However, the properties in the ST direction are better than those of the conventional AA7055-T77 alloy. Also the stress corrosion performance is better than of an AA055-T77 alloy.
  • the inventive alloy can therefore be used as an inexpensive substitute for AA7055-T77 tempered alloys which is also useable for age-creep forming, thereby showing a superior compression yield strength and corrosion resistance.

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US20060157172A1 (en) * 2005-01-19 2006-07-20 Otto Fuchs Kg Aluminum alloy that is not sensitive to quenching, as well as method for the production of a semi-finished product therefrom
US20060289093A1 (en) * 2005-05-25 2006-12-28 Howmet Corporation Al-Zn-Mg-Ag high-strength alloy for aerospace and automotive castings
US20070017604A1 (en) * 2005-05-25 2007-01-25 Howmet Corporation Al-Zn-Mg-Cu-Sc high strength alloy for aerospace and automotive castings
US20070125460A1 (en) * 2005-10-28 2007-06-07 Lin Jen C HIGH CRASHWORTHINESS Al-Si-Mg ALLOY AND METHODS FOR PRODUCING AUTOMOTIVE CASTING
US20080173377A1 (en) * 2006-07-07 2008-07-24 Aleris Aluminum Koblenz Gmbh Aa7000-series aluminum alloy products and a method of manufacturing thereof
US20080283163A1 (en) * 2007-05-14 2008-11-20 Bray Gary H Aluminum Alloy Products Having Improved Property Combinations and Method for Artificially Aging Same
US20110111081A1 (en) * 2008-06-24 2011-05-12 Aleris Aluminum Koblenz Gmbh Al-zn-mg alloy product with reduced quench sensitivity
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US20170121802A1 (en) * 2015-10-30 2017-05-04 Novelis Inc. High strength 7xxx aluminum alloys and methods of making the same
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RU2673593C1 (ru) * 2017-05-30 2018-11-28 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Высокопрочный сплав на основе алюминия
US10472707B2 (en) 2003-04-10 2019-11-12 Aleris Rolled Products Germany Gmbh Al—Zn—Mg—Cu alloy with improved damage tolerance-strength combination properties
US10835942B2 (en) 2016-08-26 2020-11-17 Shape Corp. Warm forming process and apparatus for transverse bending of an extruded aluminum beam to warm form a vehicle structural component
CN113373356A (zh) * 2021-06-21 2021-09-10 哈尔滨工程大学 一种Al-Zn-Mg-Cu-Re铝合金及其制备方法
US20220145439A1 (en) * 2020-11-11 2022-05-12 Kaiser Aluminum Fabricated Products, Llc High Strength and High Fracture Toughness 7xxx Aerospace Alloy Products
US11879166B2 (en) * 2018-11-12 2024-01-23 Novelis Koblenz Gmbh 7XXX-series aluminium alloy product
US12146202B2 (en) * 2018-07-17 2024-11-19 Constellium Neuf-Brisach Process for manufacturing thin sheets made of 7XXX aluminum alloy suitable for shaping and assembly

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US20060213591A1 (en) 2005-03-24 2006-09-28 Brooks Charles E High strength aluminum alloys and process for making the same
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CN1780925A (zh) 2006-05-31
CA2519387C (en) 2015-06-02
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DE112004000596B4 (de) 2011-03-24
US20090320969A1 (en) 2009-12-31
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