CA2519387C - 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 PDFInfo
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- CA2519387C CA2519387C CA2519387A CA2519387A CA2519387C CA 2519387 C CA2519387 C CA 2519387C CA 2519387 A CA2519387 A CA 2519387A CA 2519387 A CA2519387 A CA 2519387A CA 2519387 C CA2519387 C CA 2519387C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 176
- 239000000956 alloy Substances 0.000 title claims abstract description 176
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910001297 Zn alloy Inorganic materials 0.000 title abstract 2
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004411 aluminium Substances 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 230000032683 aging Effects 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 238000004299 exfoliation Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910018137 Al-Zn Inorganic materials 0.000 claims description 11
- 229910018573 Al—Zn Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 5
- 238000005482 strain hardening Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 9
- 239000010949 copper Substances 0.000 description 38
- 239000011777 magnesium Substances 0.000 description 34
- 239000011701 zinc Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 23
- 230000035882 stress Effects 0.000 description 19
- 239000011572 manganese Substances 0.000 description 16
- 229910052725 zinc Inorganic materials 0.000 description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229910000838 Al alloy Inorganic materials 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000002970 Calcium lactobionate Substances 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Forging (AREA)
- Heat Treatment Of Steel (AREA)
- Metal Rolling (AREA)
- Heat Treatment Of Articles (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Laminated Bodies (AREA)
- Prevention Of Electric Corrosion (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a high strength AI-Zn alloy product with an improved combination of corrosion resistance and toughness, said alloy comprising essentially (in weight percent): Zn: 6.0 - 9.5, Cu: 1.3 - 2.4, Mg:
1.5 - 2.6, Mn and Zr < 0.25 but preferably in a range between 0.05 and 0.15 for higher Zn contents, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, wherein (in weight percent): 0.1[Cu] + 1.3 < [Mg]
< 0.2[Cu] + 2.15, preferably 0.2[Cu] + 1.3 < [Mg] < 0.l[Cu] + 2.15. The invention also relates to a method to produce these alloy products, and to some preferred applications thereof such as upper wing applications in aerospace.
1.5 - 2.6, Mn and Zr < 0.25 but preferably in a range between 0.05 and 0.15 for higher Zn contents, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, wherein (in weight percent): 0.1[Cu] + 1.3 < [Mg]
< 0.2[Cu] + 2.15, preferably 0.2[Cu] + 1.3 < [Mg] < 0.l[Cu] + 2.15. The invention also relates to a method to produce these alloy products, and to some preferred applications thereof such as upper wing applications in aerospace.
Description
High strength Al-Zn alloy and method for producing such an alloy product The present invention relates to a wrought high strength Al-Zn alloy with an improved combination of corrosion resistance and toughness, a method for producing a wrought high strength Al-Zn alloy 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 having improved combinations of strength, toughness and corrosion resistance, which does not need specific ageing or temper treatments.
It is known in the art to use heat treatable aluminium alloys in a number of applications involving relatively high strength, high toughness and corrosion resistance such as aircraft fuselages, vehicular members and other applications.
Aluminium alloys AA7050 and AA7150 exhibit high strength in T6-type tempers, see e.g. US-6,315,842. 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 aircraft industry. However, 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.
In order to enhance resistance against stress corrosion and exfoliation as well as fracture toughness it is known to artificially over-age these AA7000-series alloys.
When artificially aged to a T79, T76, T74 or T73-type temper their resistance to stress corrosion, exfoliation corrosion and fracture toughness improve in the order stated (T73 being best and T79 being close to T6) but at cost to strength compared to the T6 temper condition. An acceptable temper condition is the T74-type temper, which 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. Such 174 temper is performed by
It is known in the art to use heat treatable aluminium alloys in a number of applications involving relatively high strength, high toughness and corrosion resistance such as aircraft fuselages, vehicular members and other applications.
Aluminium alloys AA7050 and AA7150 exhibit high strength in T6-type tempers, see e.g. US-6,315,842. 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 aircraft industry. However, 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.
In order to enhance resistance against stress corrosion and exfoliation as well as fracture toughness it is known to artificially over-age these AA7000-series alloys.
When artificially aged to a T79, T76, T74 or T73-type temper their resistance to stress corrosion, exfoliation corrosion and fracture toughness improve in the order stated (T73 being best and T79 being close to T6) but at cost to strength compared to the T6 temper condition. An acceptable temper condition is the T74-type temper, which 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. Such 174 temper is performed by
- 2 -over-ageing the aluminium alloy product at temperatures of 121 C for 6 to 24 hours and 171 C for about 14 hours.
Depending on the design criteria for a particular airplane component even small improvements in strength, toughness or corrosion resistance result in weight savings, which translate to fuel economy over the lifetime of the aircraft. To meet these demands several other 7000-series type alloys have been developed:
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.%:
Zn: 7.6 - 8.4 Cu: 2.2 - 2.6 Mg: 1.8 - 2.1, one or more elements selected from Zr: 0.5 - 0.2 Mn: 0.05 - 0.4 V: 0.03 - 0.2 Hf: 0.03 - 0.5, the total of said elements not exceeding 0.6 wt.%, the balance aluminium plus incidental impurities, solution heat treating and quenching said 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 or heating the product to one or more temperatures from 148 C to 174 C. These products show an improved exfoliation corrosion resistance of "EB" or better with about 15%
greater yield strength than similar sized AA7x50 counter- parts in the T76-temper condition. They still have at least about 5% greater strength than their similarly-sized 7x50-T77 counterpart (AA7150-T77 will be used herein below as a reference alloy).
US-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 stochiometrically 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
Depending on the design criteria for a particular airplane component even small improvements in strength, toughness or corrosion resistance result in weight savings, which translate to fuel economy over the lifetime of the aircraft. To meet these demands several other 7000-series type alloys have been developed:
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.%:
Zn: 7.6 - 8.4 Cu: 2.2 - 2.6 Mg: 1.8 - 2.1, one or more elements selected from Zr: 0.5 - 0.2 Mn: 0.05 - 0.4 V: 0.03 - 0.2 Hf: 0.03 - 0.5, the total of said elements not exceeding 0.6 wt.%, the balance aluminium plus incidental impurities, solution heat treating and quenching said 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 or heating the product to one or more temperatures from 148 C to 174 C. These products show an improved exfoliation corrosion resistance of "EB" or better with about 15%
greater yield strength than similar sized AA7x50 counter- parts in the T76-temper condition. They still have at least about 5% greater strength than their similarly-sized 7x50-T77 counterpart (AA7150-T77 will be used herein below as a reference alloy).
US-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 stochiometrically 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
3 PCT/EP2004/003997 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.
US-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.%:
Zn: 5.9 - 8.2 Cu: 1.5 - 3.0 Mg: 1.5 - 4.0 Cr: <0.04, other elements such as zirconium, manganese, iron, silicon and titanium in total less than 0.5, the balance aluminium, working the alloy into a product of a pre-determined shape, solution heat treating the reshaped product, quenching, and ageing the heat treated and quenched product to a temperature of from 132 C to 140 C for a period of from 6 to 30 hours. The desired properties of having high strength, high toughness and high corrosion resistance were achieved in this alloy by lowering the ageing temperature rather than raising the temperature as taught previously from e.g. US-3,881,966 or US-3,794,531.
It has been reported that the known precipitation-hardened aluminium alloys AA7075 and other AA7000-series alloys, in the T6 temper condition, have not given sufficient resistance to corrosion under certain conditions. The T7-type tempers which improve the resistance of the alloys to stress-corrosion cracking however decrease strength significantly vis-à-vis the T6 condition.
US-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.
US-5,496,426 discloses an alloy as disclosed in US-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% NaCI alternate immersion test) at 138 MPa the disclosed processed alloy had a SCC resistance of 241 MPa.
US-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.%:
Zn: 5.9 - 8.2 Cu: 1.5 - 3.0 Mg: 1.5 - 4.0 Cr: <0.04, other elements such as zirconium, manganese, iron, silicon and titanium in total less than 0.5, the balance aluminium, working the alloy into a product of a pre-determined shape, solution heat treating the reshaped product, quenching, and ageing the heat treated and quenched product to a temperature of from 132 C to 140 C for a period of from 6 to 30 hours. The desired properties of having high strength, high toughness and high corrosion resistance were achieved in this alloy by lowering the ageing temperature rather than raising the temperature as taught previously from e.g. US-3,881,966 or US-3,794,531.
It has been reported that the known precipitation-hardened aluminium alloys AA7075 and other AA7000-series alloys, in the T6 temper condition, have not given sufficient resistance to corrosion under certain conditions. The T7-type tempers which improve the resistance of the alloys to stress-corrosion cracking however decrease strength significantly vis-à-vis the T6 condition.
US-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.
US-5,496,426 discloses an alloy as disclosed in US-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% NaCI alternate immersion test) at 138 MPa the disclosed processed alloy had a SCC resistance of 241 MPa.
- 4 -US-5,108,520 and US-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. However, the three step ageing procedure is cumbersome and difficult to perform so that the costs for producing such alloy increase.
It is therefore the object of the present invention to provide an improved Al-Zn alloy preferably for plate products with high strength and an improved balance of toughness and corrosion performance. More specifically, it is the object of the is present invention to provide an alloy, which can be used for upper wing applications in aerospace with an improved compression yield strength with properties, which are better than the properties of a conventional AA7055-alloy in the 177 temper.
It is another object of the invention to obtain an AA7000-series aluminium alloy, which exhibits strength in the range of T6-type tempers and toughness and corrosion resistance properties in the range of T73-type tempers.
It is furthermore an object of the present invention to provide an alloy that can be used in an age-creep forming process, which is an alloy, which does not need a complicated or cumbersome ageing process.
The present invention has a number of preferred objects.
As will be appreciated herein below, except otherwise indicated, 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.
The above mentioned objects of the invention are achieved by using a high strength Al-Zn alloy product with an improved combination of corrosion resistance
It is therefore the object of the present invention to provide an improved Al-Zn alloy preferably for plate products with high strength and an improved balance of toughness and corrosion performance. More specifically, it is the object of the is present invention to provide an alloy, which can be used for upper wing applications in aerospace with an improved compression yield strength with properties, which are better than the properties of a conventional AA7055-alloy in the 177 temper.
It is another object of the invention to obtain an AA7000-series aluminium alloy, which exhibits strength in the range of T6-type tempers and toughness and corrosion resistance properties in the range of T73-type tempers.
It is furthermore an object of the present invention to provide an alloy that can be used in an age-creep forming process, which is an alloy, which does not need a complicated or cumbersome ageing process.
The present invention has a number of preferred objects.
As will be appreciated herein below, except otherwise indicated, 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.
The above mentioned objects of the invention are achieved by using a high strength Al-Zn alloy product with an improved combination of corrosion resistance
- 5 -and toughness, the alloy comprising essentially (in wt.%):
Zn about 6.0 to 9.5 Cu about 1.3 to 2.4 Mg about 1.5 to 2.6 Mn <012 Zr <0.20, and preferably 0.05 - 0.15 Cr <0.10 Fe <0.25, and preferably < 0.12 Si <0.25, and preferably < 0.12 Ti <0.10 Hf and/or V < 0.25, and optionally Ce and/or Sc < 0.20, especially in a range of 0.05 to 0.15, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, wherein (in weight percent):
O. 1 [CU] + 1.3 < [Mg] < 0.2[Cu] + 2.15, and preferably 0.2[Cu] + 1.3 < [Mg] < 0.1[Cu] + 2.15.
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.
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 herein below, wherein especially the exfoliation corrosion performance is enhanced.
By way of this invention it has been found that 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, toughness and corrosion performance such as exfoliation corrosion resistance and stress corrosion cracking resistance.
While it has been reported that copper contents should be maintained higher,
Zn about 6.0 to 9.5 Cu about 1.3 to 2.4 Mg about 1.5 to 2.6 Mn <012 Zr <0.20, and preferably 0.05 - 0.15 Cr <0.10 Fe <0.25, and preferably < 0.12 Si <0.25, and preferably < 0.12 Ti <0.10 Hf and/or V < 0.25, and optionally Ce and/or Sc < 0.20, especially in a range of 0.05 to 0.15, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, wherein (in weight percent):
O. 1 [CU] + 1.3 < [Mg] < 0.2[Cu] + 2.15, and preferably 0.2[Cu] + 1.3 < [Mg] < 0.1[Cu] + 2.15.
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.
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 herein below, wherein especially the exfoliation corrosion performance is enhanced.
By way of this invention it has been found that 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, toughness and corrosion performance such as exfoliation corrosion resistance and stress corrosion cracking resistance.
While it has been reported that copper contents should be maintained higher,
- 6 -preferably above about 2.2 wt.% in order to improve the exfoliation and stress corrosion cracking performance, better combinations of strength and density were reported to be achievable with relatively low zinc contents.
In this invention, however, it has been found that elevated amounts of zinc together with an optimised relation of magnesium to copper results in better strength while maintaining a good corrosion performance and a toughness which is better than conventional T77-temper alloys. It is therefore advantageous to have a combined zinc, magnesium and copper content in a range of between about 11.50 and 12.50 (in wt.%) without any manganese and below 11.00 in the presence of manganese, which is preferably between 0.06 and 0.12 (in wt.%).
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 2Ø 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.
Apart from the amounts of magnesium and copper 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 resistance properties ("EXCO") of EB or better, preferably EA or better.
These exfoliation properties are measured in accordance with the standards
In this invention, however, it has been found that elevated amounts of zinc together with an optimised relation of magnesium to copper results in better strength while maintaining a good corrosion performance and a toughness which is better than conventional T77-temper alloys. It is therefore advantageous to have a combined zinc, magnesium and copper content in a range of between about 11.50 and 12.50 (in wt.%) without any manganese and below 11.00 in the presence of manganese, which is preferably between 0.06 and 0.12 (in wt.%).
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 2Ø 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.
Apart from the amounts of magnesium and copper 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 resistance properties ("EXCO") of EB or better, preferably EA or better.
These exfoliation properties are measured in accordance with the standards
- 7 -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. To determine whether commercial alloys meet the SCC standards, a given test specimen is subjected to predefined test conditions. Bar-shaped specimens are exposed to cycles of immersing in a 3.5% NaCI 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 AA7075, AA7050 or AA7150-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 herein below.
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.
However, 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.
Some preferred embodiments of the present invention are described within the examples herein below.
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
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 AA7075, AA7050 or AA7150-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 herein below.
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.
However, 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.
Some preferred embodiments of the present invention are described within the examples herein below.
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
- 8 -a) = casting an ingot with the following composition (in weight percent):
Zn about 6.0 to 9.5 Cu about 1.3 to 2.4 Mg about 1.5 to 2.6 Mn <0.12 Zr <0.20, preferably 0.05 - 0.15 Cr <0.10 Fe <0.25 Si <0.25 Ti <0.10 Hf and/or V < 0.25, optionally Ce and/or Sc < 0.20, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, and wherein (in weight percent):
0.1[Cu] + 1.3 < [Mg] < 0.2[Cu] + 2.15, b) homogenising and/or pre-heating the ingot after casting, c) hot working the ingot and optionally cold working into a worked product, d) solution heat treating at a temperature and time sufficient to place into solid solution essentially all soluble constituents in the alloy, and e) quenching the solution heat-treated product by one of spray quenching or immersion quenching in water or other quenching media.
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.
Throughout such two-step aging treatment a corrosion performance is achieved which is similar to the corrosion performance of a T76-temper alloy.
However, it is also possible to artificially ageing the worked and heat treated product wherein 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. However, the two-step ageing procedure results in thin aluminium alloy products, which are partially comparable and partially better than T77-temper products.
Zn about 6.0 to 9.5 Cu about 1.3 to 2.4 Mg about 1.5 to 2.6 Mn <0.12 Zr <0.20, preferably 0.05 - 0.15 Cr <0.10 Fe <0.25 Si <0.25 Ti <0.10 Hf and/or V < 0.25, optionally Ce and/or Sc < 0.20, other elements each less than 0.05 and less than 0.25 in total, balance aluminium, and wherein (in weight percent):
0.1[Cu] + 1.3 < [Mg] < 0.2[Cu] + 2.15, b) homogenising and/or pre-heating the ingot after casting, c) hot working the ingot and optionally cold working into a worked product, d) solution heat treating at a temperature and time sufficient to place into solid solution essentially all soluble constituents in the alloy, and e) quenching the solution heat-treated product by one of spray quenching or immersion quenching in water or other quenching media.
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.
Throughout such two-step aging treatment a corrosion performance is achieved which is similar to the corrosion performance of a T76-temper alloy.
However, it is also possible to artificially ageing the worked and heat treated product wherein 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. However, the two-step ageing procedure results in thin aluminium alloy products, which are partially comparable and partially better than T77-temper products.
- 9 -It is furthermore possible to artificially ageing the worked and heat-treated product with a two-step ageing procedure to a 179- or T76-temper. After homogenizing and/or pre-heating the ingot after casting it is preferably advisable to hot working the ingot and optionally cold working the hot worked products into a worked product of 15 mm to 45 mm, thereby obtaining a thin plate.
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.
The foregoing and other features and advantages of the alloys according to the invention will become readily apparent from the following detailed description of preferred embodiments.
Example 1 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.
On an industrial scale four different aluminium alloys have been cast into ingots, homogenized, preheated for more than 6 hours at 410 C and hot rolled to mm plates. Thereafter, the plates were solution heat treated at 475 C and water quenched. Thereafter, the quenched product was aged by a two-step T79-T76 25 ageing procedure. The chemical compositions are set out in Table 1.
Table Chemical composition of thin plate alloys, in wt.%, balance aluminium and inevitable impurities, Alloys 1 to 4 with Mn 0.02:
Si Fe Cu Mn Mg Cr Zn Ti Zr Alloy 1 0.03 0.06 2.23 0.00 2.08 0.00 6.24 0.03 0.10 (7050) Alloy 2 0.05 0.08 2.05 0.01 2.04 0.01 6.18 0.04 0.11 Alloy 3 0.05 0.09 2.20 0.01 2.30 0.01 - 7.03 0.04 0.10 Alloy 4 0.04 0.07 1.91 0.02 2.13 0.00 6.94 0.03 0.11
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.
The foregoing and other features and advantages of the alloys according to the invention will become readily apparent from the following detailed description of preferred embodiments.
Example 1 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.
On an industrial scale four different aluminium alloys have been cast into ingots, homogenized, preheated for more than 6 hours at 410 C and hot rolled to mm plates. Thereafter, the plates were solution heat treated at 475 C and water quenched. Thereafter, the quenched product was aged by a two-step T79-T76 25 ageing procedure. The chemical compositions are set out in Table 1.
Table Chemical composition of thin plate alloys, in wt.%, balance aluminium and inevitable impurities, Alloys 1 to 4 with Mn 0.02:
Si Fe Cu Mn Mg Cr Zn Ti Zr Alloy 1 0.03 0.06 2.23 0.00 2.08 0.00 6.24 0.03 0.10 (7050) Alloy 2 0.05 0.08 2.05 0.01 2.04 0.01 6.18 0.04 0.11 Alloy 3 0.05 0.09 2.20 0.01 2.30 0.01 - 7.03 0.04 0.10 Alloy 4 0.04 0.07 1.91 0.02 2.13 0.00 6.94 0.03 0.11
- 10 -The aged alloys were thereafter tested in accordance with the following test conditions:
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, Kahn-Tear (toughness) was measured according to ASTM E-399 and the compression yield strength ("CYS") was measured according to ASTM E-9.
The results of the T79-T76 aged plate products of the four alloys as shown in Table 1 are shown in Table 2a when compared with conventional AA7150-T77 tempered alloys, and in Table 2b when compared with conventional AA7150-T76/T74/16 tempered alloys:
Table 2a Overview of strength and toughness of the alloys of Table 1 (30 mm plates) compared to three reference alloys (AA7150-T77); alloys 1 to 4 aged to T79-T76:
Rp-L CYS-LT EXCO K1-LT
(MPa) (MPa) (MPagm) Alloy 1 555 565 EC 35.1 -Alloy 2 561 604 EA/B 34.5 Alloy 3 565 590 EB 29.1 Alloy 4 591 632 EB 28.9 AA7150-T77 586 EB 28.6 AA7150-T77 579 EB 29.2 AA7150-T77 537 EA 33.2 NF = no failure after 40 days.
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, Kahn-Tear (toughness) was measured according to ASTM E-399 and the compression yield strength ("CYS") was measured according to ASTM E-9.
The results of the T79-T76 aged plate products of the four alloys as shown in Table 1 are shown in Table 2a when compared with conventional AA7150-T77 tempered alloys, and in Table 2b when compared with conventional AA7150-T76/T74/16 tempered alloys:
Table 2a Overview of strength and toughness of the alloys of Table 1 (30 mm plates) compared to three reference alloys (AA7150-T77); alloys 1 to 4 aged to T79-T76:
Rp-L CYS-LT EXCO K1-LT
(MPa) (MPa) (MPagm) Alloy 1 555 565 EC 35.1 -Alloy 2 561 604 EA/B 34.5 Alloy 3 565 590 EB 29.1 Alloy 4 591 632 EB 28.9 AA7150-T77 586 EB 28.6 AA7150-T77 579 EB 29.2 AA7150-T77 537 EA 33.2 NF = no failure after 40 days.
- 11 -Table 2b Overview of corrosion performance of the alloys of Table 1 (30 mm plates) compared to three reference alloys (AA7150-T76, AA7150-T74, AA7150-T6); alloys 1-4 aged to T79-T76:
SCC threshold Alloy 1 NF at 172 MPa Alloy 2 NF at 240 MPa Alloy 3 NF at 240 MPa Alloy 4 NF at 240 MPa AA7150-T76 117- 172 MPa AA7150-T74 240 MPa AA7150-T6 < 48 MPa NF = no failure after 40 days.
As can be seen from Table 2a,b 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 to strength than alloy No. 1 (AA7050-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 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.
Rp-L CYS-LT EXCO K1-LT SCC threshold (MPa) (MPa) (MPaqm) Alloy 2 585 613 EA 32.2 NF at 240 MPa Alloy 4 607 641 EA 26.4 NF at 240 MPa Further SCC testing was performed on the promising alloy No. 4 wherein 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
SCC threshold Alloy 1 NF at 172 MPa Alloy 2 NF at 240 MPa Alloy 3 NF at 240 MPa Alloy 4 NF at 240 MPa AA7150-T76 117- 172 MPa AA7150-T74 240 MPa AA7150-T6 < 48 MPa NF = no failure after 40 days.
As can be seen from Table 2a,b 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 to strength than alloy No. 1 (AA7050-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 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.
Rp-L CYS-LT EXCO K1-LT SCC threshold (MPa) (MPa) (MPaqm) Alloy 2 585 613 EA 32.2 NF at 240 MPa Alloy 4 607 641 EA 26.4 NF at 240 MPa Further SCC testing was performed on the promising alloy No. 4 wherein 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
- 12 -practice for evaluating stress corrosion cracking resistance of metals and alloys by alternate immersion in 3.5% NaCI solution).
Four different stress levels were chosen for samples of alloy 4 as shown in Table 4. For each stress level three samples were exposed to the test environment (ASTM G-44). One was taken out after 1 week while the other two were exposed for 40 days. When no cracking had occurred during the exposure the tensile properties were determined as shown in Table 4.
Table 4 Overview of tensile strength properties of alloy 4 after exposure to four different stress levels, pre-stress was acting in LT direction.
Alloy 4 Pre-stress Tensile strength [MPa]
[MPa] 1 week 40 days 300 524.3 428.0 340 513.1 416.9 380 503.1 424.5 420 515.5 425.1 As can be seen from Table 4, no decrease in residual strength was measured with increasing load, which means that no measurable stress corrosion appeared after 40 days as far as tensile strength properties are concerned.
Example 2 When higher strength levels are required and toughness properties are less important conventional 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 than conventional AA7055-T77 alloys.
11 different aluminium alloys were cast into ingots having the following chemical composition as set out in Table 5.
Four different stress levels were chosen for samples of alloy 4 as shown in Table 4. For each stress level three samples were exposed to the test environment (ASTM G-44). One was taken out after 1 week while the other two were exposed for 40 days. When no cracking had occurred during the exposure the tensile properties were determined as shown in Table 4.
Table 4 Overview of tensile strength properties of alloy 4 after exposure to four different stress levels, pre-stress was acting in LT direction.
Alloy 4 Pre-stress Tensile strength [MPa]
[MPa] 1 week 40 days 300 524.3 428.0 340 513.1 416.9 380 503.1 424.5 420 515.5 425.1 As can be seen from Table 4, no decrease in residual strength was measured with increasing load, which means that no measurable stress corrosion appeared after 40 days as far as tensile strength properties are concerned.
Example 2 When higher strength levels are required and toughness properties are less important conventional 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 than conventional AA7055-T77 alloys.
11 different aluminium alloys were cast into ingots having the following chemical composition as set out in Table 5.
- 13 -Table 5 Chemical composition of 11 alloys, in wt.%, balance aluminium and inevitable impurities, Zr = 0.08, Si = 0.05, Fe = 0.08.
Alloy Cu Mg Zn Mn 1 2.40 2.20 8.2 0.00 2 1.94 2.33 8.2 0.00 3 1.26 2.32 8.1 0.00 4 2.36 1.94 8.1 0.00 1.94 1.92 8.1 0.00 6 1.30 2.09 8.2 0.00 7 1.92 1.54 8.1 0.00 -8 1.27 1.57 8.1 0.00 9 2.34 2.25 8.1 0.07 2.38 2.09 8.1 0.00 11 2.35 1.53 8.2 0.00 5 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-ternper). The results are shown in Table 6.
Alloy Cu Mg Zn Mn 1 2.40 2.20 8.2 0.00 2 1.94 2.33 8.2 0.00 3 1.26 2.32 8.1 0.00 4 2.36 1.94 8.1 0.00 1.94 1.92 8.1 0.00 6 1.30 2.09 8.2 0.00 7 1.92 1.54 8.1 0.00 -8 1.27 1.57 8.1 0.00 9 2.34 2.25 8.1 0.07 2.38 2.09 8.1 0.00 11 2.35 1.53 8.2 0.00 5 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-ternper). The results are shown in Table 6.
- 14 -Table 6 Overview of strength and toughness of 11 alloys according to Table 5 in the identified directions.
Rp Rm Kq Alloy L _ LT L LT L - T
1 628 596 651 633 28.9 2 614 561 642 604 29.3 3 566 544 596 582 39.0 4 614 568 638 604 33.0 595 556 620 590 37.1 6 562 513 590 552 38.6 7 549 509 573 542 41.7 8 530 484 556 522 41.9 9 628 584 644 618 26.6 614 575 631 606 28.1 -11 568 529 594 568 36.6 5 While alloys 3 to 8 and 11 displayed good toughness properties alloys 1 to 5 and 9 and 10 displayed good strength properties. Hence, 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 10 windows.
As can be seen from 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).
Example 3 The influence of manganese was investigated on the properties of the inventive alloy. An optimum manganese level was found between 0.05 and 0.12 in alloys with a high amount of zinc. The results are shown in Tables 7 and 8.
All not mentioned chemistry properties and processing parameters are similar to those of Example 2.
Rp Rm Kq Alloy L _ LT L LT L - T
1 628 596 651 633 28.9 2 614 561 642 604 29.3 3 566 544 596 582 39.0 4 614 568 638 604 33.0 595 556 620 590 37.1 6 562 513 590 552 38.6 7 549 509 573 542 41.7 8 530 484 556 522 41.9 9 628 584 644 618 26.6 614 575 631 606 28.1 -11 568 529 594 568 36.6 5 While alloys 3 to 8 and 11 displayed good toughness properties alloys 1 to 5 and 9 and 10 displayed good strength properties. Hence, 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 10 windows.
As can be seen from 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).
Example 3 The influence of manganese was investigated on the properties of the inventive alloy. An optimum manganese level was found between 0.05 and 0.12 in alloys with a high amount of zinc. The results are shown in Tables 7 and 8.
All not mentioned chemistry properties and processing parameters are similar to those of Example 2.
- 15 -Table 7 Chemical composition of three alloys (Mn-0, Mn-1 and Mn-2), in wt.%, balance aluminium and inevitable impurities, Zr = 0.08, Si = 0.05, Fe = 0.08.
Alloy Cu Mg Zn Mn Mn-0 1.94 2.33 8.2 0.00 Mn-1 1.94 2.27 8.1 0.06 Mn-2 1.96 2.29 8.2 0.12 Table 8 Overview of strength and toughness of three alloys according to Table 7 in the identified directions.
Alloy Rp Rm Kq LT L LT L - T
Mn-O 614 561 642 604 29.3 Mn-1 612 562 635 602 31.9 Mn-2 612 560 639 596 29.9 -As shown in Table 8 the toughness properties decrease while strength properties increase. For alloys with high amounts of zinc an optimised manganese level is between 0.05 and 0.12.
Example 4 When higher strength levels are required and toughness properties are less important conventional 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.
Two different aluminium alloys were cast into ingots having the following chemical composition as set out in Table 9.
Alloy Cu Mg Zn Mn Mn-0 1.94 2.33 8.2 0.00 Mn-1 1.94 2.27 8.1 0.06 Mn-2 1.96 2.29 8.2 0.12 Table 8 Overview of strength and toughness of three alloys according to Table 7 in the identified directions.
Alloy Rp Rm Kq LT L LT L - T
Mn-O 614 561 642 604 29.3 Mn-1 612 562 635 602 31.9 Mn-2 612 560 639 596 29.9 -As shown in Table 8 the toughness properties decrease while strength properties increase. For alloys with high amounts of zinc an optimised manganese level is between 0.05 and 0.12.
Example 4 When higher strength levels are required and toughness properties are less important conventional 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.
Two different aluminium alloys were cast into ingots having the following chemical composition as set out in Table 9.
- 16 -Table 9 Chemical composition of three alloys, in wt.%, balance aluminium and inevitable impurities, Zr = 0.08, Si = 0.05, Fe = 0.08; (Ref = AA7055 alloy).
Alloy Si Fe Cu Mn Mg Cr Zn Ti Zr 1 0.05 0.09 2.24 0.01 2.37 0.01 7.89 0.04 0.10 2 0.04 0.07 1.82 0.08 2.18 0.00 8.04 0.03 0.10 Ref. 2.1- 1.8- 7.6-2.6 2.2 8.4 = 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).
Alloy Temper Rp-L Rp-LT Rp-ST Rm-L Rm-LT Rm-ST
Ref T77 614 614 634 641 M-Ref T77 621 611 - 537 638 634 599 The toughness properties in LT and TL direction as well as the compression yield strength properties in L and LT direction as well as the corrosion performance characteristics are shown in Table 11.
Alloy Si Fe Cu Mn Mg Cr Zn Ti Zr 1 0.05 0.09 2.24 0.01 2.37 0.01 7.89 0.04 0.10 2 0.04 0.07 1.82 0.08 2.18 0.00 8.04 0.03 0.10 Ref. 2.1- 1.8- 7.6-2.6 2.2 8.4 = 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).
Alloy Temper Rp-L Rp-LT Rp-ST Rm-L Rm-LT Rm-ST
Ref T77 614 614 634 641 M-Ref T77 621 611 - 537 638 634 599 The toughness properties in LT and TL direction as well as the compression yield strength properties in L and LT direction as well as the corrosion performance characteristics are shown in Table 11.
- 17 -Table 11 Toughness and CYS properties of the two inventive alloys of Table 9 in different temper conditions and different test directions, NF = no failure after 40 days at designated stress levels, otherwise days are stated after which the specimen failed.
Alloy Temper K1 K1 CYS-L CYS-LT EXCO SCC
(L-T) (T-L) 1 T79-T76 21.0 596 621 EC 2,3,8 2 T79-T76 28.9 27.1 630 660 EB NF at 172MPa 2 T77 28.8 26.5 628 656 EA NF at 210MPa Ref 177 28.6 26.4 621 648 EB NF at 10N3FMaPt a M-Ref T77 EB
103MPa The inventive alloy has similar tensile properties as a conventional AA7055-177 alloy. However, the properties in the ST direction are better than those of the conventional AA7055-177 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.
The scope of the claims should not be limited by the specific embodiments set forth herein, but should be given the broadest interpretation consistent with the description as a whole.
Alloy Temper K1 K1 CYS-L CYS-LT EXCO SCC
(L-T) (T-L) 1 T79-T76 21.0 596 621 EC 2,3,8 2 T79-T76 28.9 27.1 630 660 EB NF at 172MPa 2 T77 28.8 26.5 628 656 EA NF at 210MPa Ref 177 28.6 26.4 621 648 EB NF at 10N3FMaPt a M-Ref T77 EB
103MPa The inventive alloy has similar tensile properties as a conventional AA7055-177 alloy. However, the properties in the ST direction are better than those of the conventional AA7055-177 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.
The scope of the claims should not be limited by the specific embodiments set forth herein, but should be given the broadest interpretation consistent with the description as a whole.
Claims (23)
1. A wrought high-strength Al-Zn alloy product, said alloy comprising essentially of, in weight percent:
Zn 8.1 to 9.5 Cu 1.93 to 2.4 Mg 1.93 to 2.6 Mn 0.06 to 0.12 Zr < 0.20 Cr < 0.10 Fe < 0.25 Si < 0.25 Ti < 0.10 Hf and/or V < 0.25, and unavoidable impurities each less than 0.05 weight percent and less than 0.25 weight percent in total, balance aluminium, and wherein, in weight percent:
0.1[Cu]+1.3<[Mg]<0.2[Cu]+2.15, wherein the alloy has been artificially aged to a T79 or T76 temper in a two-step ageing procedure, and wherein the product is a plate product having a thickness in a range of 15 to 45 mm.
Zn 8.1 to 9.5 Cu 1.93 to 2.4 Mg 1.93 to 2.6 Mn 0.06 to 0.12 Zr < 0.20 Cr < 0.10 Fe < 0.25 Si < 0.25 Ti < 0.10 Hf and/or V < 0.25, and unavoidable impurities each less than 0.05 weight percent and less than 0.25 weight percent in total, balance aluminium, and wherein, in weight percent:
0.1[Cu]+1.3<[Mg]<0.2[Cu]+2.15, wherein the alloy has been artificially aged to a T79 or T76 temper in a two-step ageing procedure, and wherein the product is a plate product having a thickness in a range of 15 to 45 mm.
2. Alloy according to claim 1, wherein the alloy further comprises Ce and/or Sc in an amount of < 0.20 wt.%.
3. Alloy according to claim 1, wherein the amount of Mg, in weight percent, is in a range of 0.2[Cu]+1.3<[Mg]<0.1[Cu]+2.15.
4. Alloy according to claim 1, wherein the amount of Mg, in weight percent, is in a range of 0.2[Cu]+1.4<[Mg]<0.1[Cu]+1.9.
5. Alloy according to claim 1, wherein the alloy product has an exfoliation corrosion resistance ("EXCO") of EB or better.
6. Alloy according to claim 1, wherein the alloy product has an exfoliation corrosion resistance ("EXCO") of EA or better.
7. Alloy according to claim 1, wherein the amount of Cu, in weight percent, is in a range of 1.93 to 2.1.
8. Alloy according to claim 1, wherein the amount of Cu, in weight percent, is in a range of 1.93 to 2Ø
9. Alloy according to claim 1, wherein the amount of Zr, in weight percent, is in a range of 0.05 to 0.15.
10. Alloy according to claim 1, wherein the amount of Fe, in weight percent, is less than 0.12.
11. Alloy according to claim 1, wherein the amount of Si, in weight percent, is less than 0.12.
12. Alloy according to claim 1, wherein the two-step ageing procedure consists of a first heat treatment at a temperature in a range of 105°C to 135°C for 2 to 20 hours, and a second heat treatment at a higher temperature than 135°C but below 210°C for 4 to 12 hours.
13. Alloy according to claim 1, wherein the plate product is an aircraft member.
14. Alloy according to claim 1, wherein the plate product is an elongate structural shape member of an aircraft.
15. Alloy according to claim 1, wherein the plate product is an upper-wing member of an aircraft.
16. Alloy according to claim 1, wherein the plate product is a skin member of an upper-wing of an aircraft.
17. Alloy according to claim 1, wherein the plate product is a stringer of an aircraft.
18. Alloy according to claim 1, wherein the plate product is a stringer of an upper-wing of an aircraft.
19. Method for producing a wrought high-strength Al-Zn alloy product according to claim 1, comprising the steps of:
a) casting an ingot with the following composition, in weight percent:
Zn 8.1 to 9.5 Cu 1.93 to 2.4 Mg 1.93 to 2.6 Mn 0.06 to 0.12 Zr < 0.20 Cr < 0.10 Fe < 0.25 Si < 0.25 Ti < 0.10 Hf and/or V < 0.25, unavoidable impurities each less than 0.05 weight percent and less than 0.25 weight percent in total, balance aluminium, wherein, in weight percent:
0.1[Cu]+1.3<[Mg]<0.2[Cu]+2.15, b) homogenising and/or pre-heating the ingot after casting, c) hot working the ingot into a worked product having a thickness in the range of 15 mm to 45 mm, d) solution heat treating and e) quenching the solution heat-treated product, and f) artificially ageing the worked and solution heat treated product with a two step ageing procedure to a T79 or T76 temper.
a) casting an ingot with the following composition, in weight percent:
Zn 8.1 to 9.5 Cu 1.93 to 2.4 Mg 1.93 to 2.6 Mn 0.06 to 0.12 Zr < 0.20 Cr < 0.10 Fe < 0.25 Si < 0.25 Ti < 0.10 Hf and/or V < 0.25, unavoidable impurities each less than 0.05 weight percent and less than 0.25 weight percent in total, balance aluminium, wherein, in weight percent:
0.1[Cu]+1.3<[Mg]<0.2[Cu]+2.15, b) homogenising and/or pre-heating the ingot after casting, c) hot working the ingot into a worked product having a thickness in the range of 15 mm to 45 mm, d) solution heat treating and e) quenching the solution heat-treated product, and f) artificially ageing the worked and solution heat treated product with a two step ageing procedure to a T79 or T76 temper.
20. Method according to claim 19, wherein step c) further comprises cold working the ingot into a worked product.
21. Method according to claim 19, wherein the ingot of step a) further comprises Ce and/or Sc in an amount of < 0.20 wt.%.
22. Method according to claim 19, wherein Zr is in the range of 0.05 - 0.15 weight percent.
23. Method according to claim 19, wherein the ageing step comprises a first heat treatment at a temperature in a range of 105°C to 135°C for 2 to 20 hours, and a second heat treatment at a higher temperature than 135°C
but below 210°C for 4 to 12 hours.
but below 210°C for 4 to 12 hours.
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2004
- 2004-04-07 US US10/819,130 patent/US20050034794A1/en not_active Abandoned
- 2004-04-09 GB GB0520502A patent/GB2415203B/en not_active Expired - Lifetime
- 2004-04-09 ES ES200550065A patent/ES2288389A1/en active Pending
- 2004-04-09 RU RU2005134846/02A patent/RU2353699C2/en active
- 2004-04-09 FR FR0403746A patent/FR2853666B1/en not_active Expired - Lifetime
- 2004-04-09 CA CA2519387A patent/CA2519387C/en not_active Expired - Lifetime
- 2004-04-09 DE DE112004000596T patent/DE112004000596B4/en not_active Revoked
- 2004-04-09 WO PCT/EP2004/003997 patent/WO2004090183A1/en not_active Application Discontinuation
- 2004-04-09 AT AT0911004A patent/AT502294B1/en not_active IP Right Cessation
- 2004-04-09 CA CA2881183A patent/CA2881183C/en not_active Expired - Lifetime
- 2004-04-09 CN CN201310039039.XA patent/CN103146969B/en not_active Expired - Lifetime
- 2004-04-09 JP JP2006505139A patent/JP4964586B2/en not_active Expired - Lifetime
- 2004-04-09 BR BRPI0409360-7A patent/BRPI0409360A/en not_active Application Discontinuation
- 2004-04-09 ES ES201131194A patent/ES2398002B2/en not_active Expired - Fee Related
- 2004-04-09 CN CN200480009567.XA patent/CN1780925B/en not_active Expired - Lifetime
-
2009
- 2009-08-25 US US12/547,466 patent/US20090320969A1/en not_active Abandoned
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RU2005134846A (en) | 2006-04-10 |
ES2398002A1 (en) | 2013-03-13 |
GB2415203B (en) | 2007-01-03 |
JP4964586B2 (en) | 2012-07-04 |
US20090320969A1 (en) | 2009-12-31 |
DE112004000596B4 (en) | 2011-03-24 |
WO2004090183A1 (en) | 2004-10-21 |
JP2006522872A (en) | 2006-10-05 |
DE112004000596T5 (en) | 2006-03-09 |
FR2853666A1 (en) | 2004-10-15 |
CA2881183A1 (en) | 2004-10-21 |
CN103146969B (en) | 2015-07-08 |
US20050034794A1 (en) | 2005-02-17 |
CA2881183C (en) | 2018-06-12 |
CA2519387A1 (en) | 2004-10-21 |
CN1780925A (en) | 2006-05-31 |
CN103146969A (en) | 2013-06-12 |
FR2853666B1 (en) | 2007-05-11 |
CN1780925B (en) | 2013-03-27 |
BRPI0409360A (en) | 2006-04-25 |
RU2353699C2 (en) | 2009-04-27 |
AT502294B1 (en) | 2010-02-15 |
GB2415203A (en) | 2005-12-21 |
AT502294A1 (en) | 2007-02-15 |
ES2288389A1 (en) | 2008-01-01 |
GB0520502D0 (en) | 2005-11-16 |
ES2398002B2 (en) | 2015-01-22 |
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