EP1831415B2 - Herstellungsverfahren für ein hochfestes, hochzähes a1-zinnlegierungsprodukt - Google Patents

Herstellungsverfahren für ein hochfestes, hochzähes a1-zinnlegierungsprodukt Download PDF

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Publication number
EP1831415B2
EP1831415B2 EP05802352.4A EP05802352A EP1831415B2 EP 1831415 B2 EP1831415 B2 EP 1831415B2 EP 05802352 A EP05802352 A EP 05802352A EP 1831415 B2 EP1831415 B2 EP 1831415B2
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Prior art keywords
product
range
temper
ageing
alloy
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French (fr)
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EP1831415A1 (de
EP1831415B1 (de
Inventor
Rinze Benedictus
Christian Joachim Keidel
Alfred Ludwig Heinz
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Novelis Koblenz GmbH
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Aleris Aluminum Koblenz GmbH
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Classifications

    • 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 high-strength high-toughness AI-Zn alloy wrought product with elevated amounts of Zn for maintaining good corrosion resistance, and to a method for producing such a high-strength high-toughness AI-Zn alloy product and to a plate product of such alloy. More specifically, the present invention relates to a high strength, high toughness AI-Zn alloy designated by the AA7000-series of the international nomenclature of the Aluminum Association for structural aeronautical applications. Even more specifically, the present invention relates to a new chemistry window for an AI-Zn alloy having improved combinations of strength and toughness by maintaining good corrosion resistance, which does not need specific ageing or temper treatments.
  • Aluminium alloys AA7050 and AA7150 exhibit high strength in T6-type tempers. Also precipitation-hardened AA7x75, 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 aerospace 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 followed by 171°C for about 14 hours.
  • each of EP-0377779 , EP 0 368 005 , US-5,221,377 and US-5,496,426 disclose alloy products and an improved process for producing an 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, about in wt.%: Zn 7.6 to 8.4, Cu 2.2 to 2.6, Mg 1.8 to 2.1 or 2.2, and one or more elements selected from Zr, Mn V and Hf, the total of the elements not exceeding 0.6 wt.%, the balance aluminium plus incidental impurities, solution heat treating and quenching the product and artificially ageing the product by either heating the product three times in a row to one or more temperatures from 79°C to 163°C or heating such product first to one or more temperatures from 79°C to 141°C for two hours or more and heating the product to one or more temperatures from 148°C to 174°C.
  • 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.
  • an AI-Zn alloy product with an improved combination of high toughness and high strength by maintaining good corrosion resistance
  • said alloy comprising, and preferably consisting of, (in weight percent): Zn 6.0 to 11.0 Cu 1.4 to 2.2 Mg 1.4 to 2.4 Zr 0.05 to 0.15 Ti ⁇ 0.05, Hf and/or V ⁇ 0.25, optionally Sc and/or Ce 0.05 to 0.25, and optionally Mn 0.05 to 0.12, and inevitable impurities and balance aluminium, preferably other elements each less than 0.05 and less than 0.50 in total, and wherein the alloy product has a substantially fully unrecrystallized microstructure at the position T/10 of the finished product.
  • Such chemistry window for an AA7000-series alloy exhibits excellent properties when produced to relatively thin plate products, and which is preferably useable in aerospace upper-wing applications having gauges in the range of 20 mm to 60 mm.
  • 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 three-step ageing cycles.
  • the chemistry leads to an aluminium product which is more cost effective and is also simpler to produce since less processing steps are necessary. Additionally, the chemistry allows new manufacturing techniques like age forming or 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 whereby the corrosion resistance further improves.
  • a selected range of elements using a higher amount of Zn and a specific combination of a particular range of Mg and Cu, exhibit substantially better combinations of strength and toughness and maintaining a good corrosion performance such as exfoliation corrosion resistance and stress corrosion cracking resistance.
  • the present invention uses the chemistry in combination with a method to produce a rolled product from such chemistry, as explained herein below, to obtain a substantially fully unrecrystallized microstructure at least at the position T/10 of the finished product. More preferably the product is unrecystallized across the whole thickness. With unrecystallized we mean that more than 80%, preferably more than 90% of the gauge of the finished rolled product is substantially unrecrystallized.
  • the present invention is disclosing an alloy product which is in particular suitable for upper wing skin applications for aircrafts and having a thickness in the range of 20 to 60 mm, preferably 30 to 50 mm.
  • 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 while 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 1.7 and 2.2%, preferably between 1.7 and 2.1% for Mg and 1.8 and 2.1% for Cu have been found to give a good balance for thin plate products. 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 invention discloses a balance of magnesium and copper amounts to zinc, especially the balance of magnesium to zinc, which gives the alloy these performance characteristics.
  • the improved corrosion resistance of the alloy according to the invention has exfoliation properties ("EXCO") of EB or better, preferably EA or better.
  • the amount (in weight%) of zinc is preferably in a range of 7.4 to 9.6%, more preferably in a range of 8.0 to 9.6%, most preferably in a range of 8.4 to 8.9%. Testing has found an optimum zinc level of about 8.6%. Further details are given in the examples as described in more details hereinbelow.
  • a Sc-containing alloy is an excellent candidate for obtaining high strength versus high notch toughness levels.
  • Sc is in a range of [Zr] + 1.5 [Sc] ⁇ 0.15%.
  • Preferred amounts (in weight%) of Sc or Ce are in a range of 0.03 to 0.06% when the amount of Zn is about 8.70% and Mg and Cu are about 2.10%. The levels of the unit propagation energy are considerably good for an alloy with additional Sc, Ce or Mn alloying elements.
  • a method for producing a high strength, high toughness AI-Zn alloy product with good corrosion resistance comprises the steps of claim 1.
  • microstructure of the alloy product remains substantially fully unrecrystallized underneath its surface when the inventive method step of pre-working the product and hot rolling and cold rolling the pre-worked product are applied.
  • the method includes a first hot rolling of the ingot which has been homogenised into a pre-worked product, hot rolling the re-heated product to about 150 to 250 (in final-gauge%) and then cold rolling the hot rolled product to the final gauge or hot rolling the re-heated product to about 105 to 140 (in final-gauge%) and then cold rolling the hot rolled product to the final gauge.
  • "Final-gauge%” means a percentage in thickness compared to the thickness of the final product. 200 final-gauge% means a thickness which is twice as much as the thickness of the finally worked product.
  • the present invention it is advantageous to hot roll the re-heated product at low temperatures in the range of 300°C to 420°C so that the alloy does not recrystallise.
  • the present invention is useful for hot-working the ingot after casting and cold-working into a worked product with a gauge in the range of 20 to 60 mm.
  • the present invention also concerns a plate product of high strength, high toughness AI-Zn alloy of the aforementioned composition which plate product is preferably a thin aircraft member, even more preferably an elongate structural shape member such as an upper-wing member, a thin skin member of an upper-wing or of a stringer of an aircraft.
  • the properties of the claimed alloy may further be enhanced by an artificial ageing step comprising 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 then 135°C but below 210°C, preferably around 155°C for 4 to 12 hours, preferably 8 to 10 hours.
  • an artificial ageing step comprising 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 then 135°C but below 210°C, preferably around 155°C for 4 to 12 hours, preferably 8 to 10 hours.
  • step 5 variant 1 being comparative examples and variants 2 and 3 being examples of the invention
  • Sc-containing alloy 14 is advantageous if high strength versus high notch toughness is needed. Small amounts of manganese do increase the strength but at the cost of some toughness.
  • the toughness versus tensile yield strength (Rp) shown in Table 4 clearly shows that the best toughness versus tensile yield strength value is obtained for alloys having around 8.6 to 8.7 weight% zinc. Alloys with lower levels of zinc will show similar toughness values but the tensile strength is -generally speaking- lower whereas high levels of zinc result in higher strength levels but lower toughness levels. Small amounts of manganese do increase the strength at the cost of toughness.
  • magnesium levels are of less than 2.4% with an optimum of about 1.7%.
  • magnesium levels are at about 1.7%, excellent toughness properties are obtained but the strength levels decrease.
  • magnesium levels of about 2.1% the best strength levels are obtained.
  • magnesium is best in between 1.7 and 2.1%.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Metal Rolling (AREA)
  • Forging (AREA)
  • Powder Metallurgy (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Claims (18)

  1. Verfahren zur Herstellung eines hochfesten, hochzähen Al-Zn-Legierungsprodukts mit guter Korrosionsbeständigkeit, umfassend die Schritte:
    a.) (Guss)Formen eines Barrens mit der folgenden Zusammensetzung, in Gewichtsprozent:
    Zn 6,0 bis 11,0%
    Cu 1,4 bis 2,2%
    Mg 1,4 bis 2,4%
    Zr 0,05 bis 0,15%
    Ti < 0,05%
    Hf und/oder V < 0,25%,
    wahlweise Sc und/oder Ce 0,05 bis 0,25%,
    wahlweise Mn 0,05 bis 0,12%, und
    unvermeidbare Verunreinigungen und Rest Aluminium,
    b.) Homogenisieren und/oder Vorwärmen des Barrens nach dem Formen,
    c.) Warmbearbeiten des Barrens zu einem vorbearbeiteten Produkt,
    d.) Wiedererwärmen des vorbearbeiteten Produkts und Warmwalzen des nacherwärmten Produkts, Kaltwalzen des warmgewalzten Produkts um ein Maß von 10 bis 20% auf Enddicke,
    e.) Lösungsglühen und Abschrecken des lösungsgeglühten Produkts,
    f.) optional Recken oder Komprimieren des abgeschreckten Legierungsprodukts, und
    g.) optional Altern des abgeschreckten und ggf. gereckten oder komprimierten Produkts, um einen gewünschten Zustand bzw. Temper zu erzielen,
    und wobei das Produkt in seinem Endzustand eine im Wesentlichen vollständig nicht rekristallisierte Mikrostruktur zumindest an der Position T/10 des fertigen Produkts aufweist.
  2. Verfahren nach Anspruch 1, wobei das Warmwalzen des nacherwärmten Produkts auf etwa 150 bis 250 (in Prozent der Enddicke) und dann das Kaltwalzen des warmgewalzten Produkts auf die Enddicke erfolgen.
  3. Verfahren nach Anspruch 1 oder 2, wobei das Warmwalzen des nacherwärmten Produkts auf etwa 105 bis 140 (in Prozent des Endmaßes) und dann das Kaltwalzen des warmgewalzten Produkts auf die Enddicke erfolgen.
  4. Verfahren nach einem der Ansprüche 1 bis 3, umfassend das Warmwalzen des nacherwärmten Produkts bei niedrigen Temperaturen im Bereich von 300°C bis 420°C, um das Legierungsprodukt am Rekristallisieren zu hindern.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das künstliche Altern während Schritt g.) im Tempern besteht, ausgewählt aus der Gruppe bestehend aus T79 und T76, und bevorzugt mithilfe einer zweistufigen Alterungsbehandlung.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das künstliche Altern während Schritt g.) aus einem ersten Alterungsschritt besteht bei einer Temperatur in einem Bereich von 105 bis 135°C während 2 bis 20 Stunden und einem zweiten Alterungsschritt bei einer Temperatur über 135°C, aber unter 210°C während 4 bis 12 Stunden bis zu einem Zustand bzw. Temper ausgewählt aus T79- und T76-Temper.
  7. Verfahren nach Anspruch 6, wobei das künstliche Altern während Schritt g.) aus einem ersten Alterungsschritt besteht bei einer Temperatur um 120°C während 2 bis 20 Stunden und aus einem zweiten Alterungsschritt bei einer Temperatur über 135°C, aber unter 210°C während 4 bis 12 Stunden bis zu einem Temper ausgewählt aus T79- und T76-Temper.
  8. Verfahren nach Anspruch 6 oder 7, wobei das künstliche Altern während Schritt g.) aus einem ersten Alterungsschritt besteht bei einer Temperatur um 120°C während 2 bis 20 Stunden und aus einem zweiten Alterungsschritt bei einer Temperatur um 155°C während 4 bis 12 Stunden bis zu einem Temper ausgewählt aus T79- und T76-Temper.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die Menge an Zn in einem Bereich von 7,4 bis 9,6 Gew.-% liegt.
  10. Verfahren nach Anspruch 9, wobei die Menge an Zn in einem Bereich von 8,0 bis 9,6 Gew.-% liegt, und bevorzugt in einem Bereich von 8,4 bis 8,9 Gew.-%.
  11. Verfahren nach einem der Ansprüche 1 bis 10, wobei die Menge an Cu in einem Bereich von 1,7 bis 2,2 Gew.-% liegt, und bevorzugt in einem Bereich von 1,8 bis 2,1 Gew.-%.
  12. Verfahren nach Anspruch 11, wobei die Menge an Mg in einem Bereich von 1,7 bis 2,2 Gew.-% liegt, und bevorzugt in einem Bereich von 1,7 bis 2,1 Gew.-%.
  13. Verfahren nach einem der Ansprüche 1 bis 12, wobei die Menge an Sc in einem Bereich von [Zr]+1,5[Sc]<0,15 Gew.-% liegt.
  14. Verfahren nach einem der Ansprüche 1 bis 13, wobei die Menge an Sc in einem Bereich von 0,03 bis 0,06% liegt, und wobei die Menge an Ce in einem Bereich von 0,03 bis 0,06% liegt.
  15. Verfahren nach einem der Ansprüche 1 bis 14, wobei die Menge an unvermeidbaren Verunreinigungen jeweils <0,05 Gew.-% und insgesamt <0,5 Gew.-% beträgt.
  16. Verfahren nach einem der Ansprüche 1 bis 15, wobei über 80%, und bevorzugt über 90%, der Dicke bzw. des Maßes des fertigen gewalzten Produkts eine im Wesentlichen nicht rekristallisierte Mikrostruktur aufweisen.
  17. Verfahren nach einem der Ansprüche 1 bis 16, wobei das Al-Zn-Produkt eine dünne Platte mit einer Dicke im Bereich von 20 bis 60 mm, und bevorzugt 30 bis 50 mm, ist.
  18. Verfahren nach einem der Ansprüche 1 bis 17, wobei das Al-Zn-Produkt ein Produkt ist ausgewählt aus der Gruppe bestehend aus einem dünnen Flugzeugteil, einem Teil der oberen Tragfläche, einem dünnen Hautteil der oberen Tragfläche oder einem Längs(versteifungs)träger eines Flugzeugs.
EP05802352.4A 2004-10-05 2005-10-04 Herstellungsverfahren für ein hochfestes, hochzähes a1-zinnlegierungsprodukt Active EP1831415B2 (de)

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Application Number Priority Date Filing Date Title
EP04077721 2004-10-05
PCT/EP2005/010809 WO2006037648A1 (en) 2004-10-05 2005-10-04 HIGH STRENGTH, HIGH TOUGHNESS Al-Zn ALLOY PRODUCT AND METHOD FOR PRODUCING SUCH PRODUCT
EP05802352.4A EP1831415B2 (de) 2004-10-05 2005-10-04 Herstellungsverfahren für ein hochfestes, hochzähes a1-zinnlegierungsprodukt

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EP1831415A1 EP1831415A1 (de) 2007-09-12
EP1831415B1 EP1831415B1 (de) 2009-03-18
EP1831415B2 true EP1831415B2 (de) 2014-10-15

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EP (1) EP1831415B2 (de)
JP (1) JP5068654B2 (de)
CN (1) CN101068943B (de)
AT (1) ATE426050T1 (de)
BR (1) BRPI0517538B1 (de)
CA (1) CA2592132C (de)
DE (2) DE102005045341A1 (de)
FR (1) FR2876118B1 (de)
RU (1) RU2404276C2 (de)
WO (1) WO2006037648A1 (de)

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EP1831415A1 (de) 2007-09-12
RU2404276C2 (ru) 2010-11-20
CN101068943B (zh) 2011-11-23
JP5068654B2 (ja) 2012-11-07
FR2876118A1 (fr) 2006-04-07
CN101068943A (zh) 2007-11-07
FR2876118B1 (fr) 2010-08-20
RU2007116979A (ru) 2008-11-20
EP1831415B1 (de) 2009-03-18
BRPI0517538A (pt) 2008-10-14
DE102005045341A1 (de) 2006-07-20
DE602005013429D1 (de) 2009-04-30
WO2006037648A1 (en) 2006-04-13
ATE426050T1 (de) 2009-04-15
JP2008516079A (ja) 2008-05-15
BRPI0517538B1 (pt) 2015-06-16
CA2592132A1 (en) 2006-04-13
CA2592132C (en) 2014-08-05

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