WO2019046275A1 - Produits en alliage d'aluminium de série 7xxx dans un état de revenu t4 stabilisé et leurs procédés de fabrication - Google Patents
Produits en alliage d'aluminium de série 7xxx dans un état de revenu t4 stabilisé et leurs procédés de fabrication Download PDFInfo
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- WO2019046275A1 WO2019046275A1 PCT/US2018/048305 US2018048305W WO2019046275A1 WO 2019046275 A1 WO2019046275 A1 WO 2019046275A1 US 2018048305 W US2018048305 W US 2018048305W WO 2019046275 A1 WO2019046275 A1 WO 2019046275A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—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 magnesium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/003—Aluminium alloys
Definitions
- the present disclosure generally provides 7xxx series aluminum alloy products in a stable T4 temper.
- the disclosure also provides methods of making such products, for example, using processes that include a combination of casting, rolling, solutionizing, quenching, reheating, and slow cooling.
- the disclosure also provides various end uses of such products, such as in automotive, transportation, electronics, and industrial applications.
- Aluminum alloys of the 7xxx series are used in a number of contexts, especially where high strength and light weight are particularly desirable. For that reason, such alloys are frequently used in the aerospace industry and as encasements for various electronic products, such as cellular phones. Notwithstanding these advantages, the process of forming 7xxx series aluminum alloys can pose certain challenges, which can increase the costs of using such alloys in certain manufactured goods.
- 7xxx series aluminum alloy products are often supplied to users in an F temper, meaning that it is supplied in an as-fabricated form, where, for example, no solutionizing is performed after the rolling process. Users must therefore solutionize the product themselves and form it into a manufactured product by a hot forming process.
- 7xxx series aluminum alloy products are supplied to users in a T6 temper, where the aluminum alloy product undergoes solutionizing followed by artificial aging. Users can generally form such products at room temperature, but their formability is quite low.
- the present disclosure provides novel 7xxx series aluminum alloy products in a T4 temper that is stable for a substantial period of time, for example, up to 6 months, before beginning to harden and thereby losing formability. Because these products are able to retain the formability benefits of this T4 temper for such a long period of time, they can be readily incorporated into manufacturing production cycles. This was impossible for previously known 7xxx series aluminum alloy products in a T4 temper, as those products generally began to harden and lose formability within mere days of their production. By the time the aluminum alloy product arrived at a buyer's plant, the material would likely have lost the beneficial formability properties it once possessed. Thus, the discovery of a 7xxx series aluminum alloy product in a stable T4 temper offers a significant advancement in the state of the art, and allows such materials to be incorporated into products of manufacture with greater ease and at much lower costs.
- the disclosure provides a method of making a rolled aluminum alloy product, comprising providing a 7xxx series aluminum alloy, wherein the 7xxx series aluminum alloy is a molten 7xxx series aluminum alloy; casting the molten 7xxx series aluminum alloy to provide an aluminum alloy cast product; homogenizing the aluminum alloy cast product to provide a homogenized aluminum alloy cast product; rolling the homogenized aluminum alloy cast product to form a rolled aluminum alloy product; and solutionizing and, then, pre-aging, the rolled aluminum alloy product.
- the aluminum alloy product is a strip, a shate, a sheet, a plate, a billet, or other aluminum alloy product.
- the rolled aluminum alloy product exhibits an increase in its yield strength (Rp) of no more than 25 MPa during a post-production period immediately following the pre- aging, wherein the post-production period ranges from 15 days to 180 days.
- the disclosure provides an aluminum alloy product, wherein the aluminum alloy product is a rolled aluminum alloy product made according to the methods of the first aspect, including any embodiments thereof.
- the disclosure provides an article of manufacture, which comprises an aluminum alloy product of the second aspect, and any embodiments thereof.
- FIG. 1 shows the change in the yield strength (Rp) as a function of the number of days following initial production for aluminum alloy samples prepared with and without pre- aging (PX).
- FIG. 2 shows the change in the yield strength (Rp) as a function of the number of days following initial production for aluminum alloy samples prepared without pre-aging (PX) and with pre-aging under various conditions.
- FIGS. 3A-C show the change in yield strength (Rp) for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- FIGS. 4A-C show the change in elongation strength for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- FIGS. 5A-C show the change in uniform elongation for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- FIGS. 6A-C show the change in total elongation for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- FIGS. 7A-D show the change in critical fracture strain for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- FIGS. 8A-D show the change in n-value for aluminum alloy samples as a function of pre-aging time, pre-aging temperature, and whether a paint bake cycle was used.
- the present disclosure provides 7xxx series aluminum alloy products that are in a stable T4 temper following solutionizing and pre-aging, and methods of making the same. These products can be easily formed at room temperature for a substantial period of time following pre-aging.
- a "plate” generally has a thickness of greater than about 15 mm.
- a plate may refer to an aluminum product having a thickness of greater than about 15 mm, greater than about 20 mm, greater than about 25 mm, greater than about 30 mm, greater than about 35 mm, greater than about 40 mm, greater than about 45 mm, greater than about 50 mm, or greater than about 100 mm.
- a “shate” (also referred to as a sheet plate) generally has a thickness of from about 4 mm to about 15 mm.
- a shate may have a thickness of about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm, about 12 mm, about 13 mm, about 14 mm, or about 15 mm.
- a "sheet” generally has a thickness of less than 4 mm.
- a sheet may have a thickness of less than about 4 mm, less than about 3 mm, less than about 2 mm, less than about 1 mm, less than about 0.5 mm, less than about 0.3 mm, or less than about 0.1 mm.
- alloy temper or condition For an understanding of the alloy temper descriptions most commonly used, see “American National Standards (ANSI) H35 on Alloy and Temper Designation Systems.”
- An F condition or temper refers to an aluminum alloy as fabricated.
- An O condition or temper refers to an aluminum alloy after annealing.
- An Hxx condition or temper also referred to herein as an H temper, refers to an aluminum alloy after cold rolling with or without thermal treatment (e.g., annealing).
- Suitable H tempers include HX1, HX2, HX3 HX4, HX5, HX6, HX7, HX8, or HX9 tempers, along with Hxxx temper variations (e.g., HI 11), which are used for a particular alloy temper when the degree of temper is close to the Hxx temper.
- a Tl condition or temper refers to an aluminum alloy cooled from hot working and naturally aged (e.g., at ambient temperature).
- a T2 condition or temper refers to an aluminum alloy cooled from hot working, cold worked and naturally aged.
- a T3 condition or temper refers to an aluminum alloy solution heat treated, cold worked, and naturally aged.
- a T4 condition or temper refers to an aluminum alloy solution heat treated and naturally aged.
- a T5 condition or temper refers to an aluminum alloy cooled from hot working and artificially aged (at elevated temperatures).
- a T6 condition or temper refers to an aluminum alloy solution heat treated, quenched, and artificially aged.
- a T61 condition or temper refers to an aluminum alloy solution heat treated, quenched, naturally aged for a period of time, and then artificially aged.
- a T7 condition or temper refers to an aluminum alloy solution heat treated and artificially overaged.
- a T8x condition or temper (e.g., T8) refers to an aluminum alloy solution heat treated, cold worked, and artificially aged.
- a T9x condition or temper refers to an aluminum alloy solution heat treated, artificially aged, and cold worked.
- the following aluminum alloys are described in terms of their elemental composition in weight percentage (wt. %) based on the total weight of the alloy. In certain examples of each alloy, the remainder is aluminum, with a maximum wt. % of 0.15 % for the sum of the impurities.
- room temperature can include a temperature of from about 15 °C to about 30 °C, for example about 15 °C, about 16 °C, about 17 °C, about 18 °C, about 19 °C, about 20 °C, about 21 °C, about 22 °C, about 23 °C, about 24 °C, about 25 °C, about 26 °C, about 27 °C, about 28 °C, about 29 °C, or about 30 °C.
- cast product refers to a product produced by direct chill casting (including direct chill co-casting) or semi -continuous casting, continuous casting (including, for example, by use of a twin belt caster, a twin roll caster, a block caster, or any other continuous caster), electromagnetic casting, hot top casting, or any other casting method.
- the methods and products disclosed herein generally use 7xxx series aluminum alloys.
- such alloys are aluminum alloys that include Zn as the major alloying element.
- Any suitable 7xxx series aluminum alloy can be used in the methods and products disclosed herein.
- such 7xxx series aluminum alloys include, but are not limited to, the following 7xxx series aluminum alloys: AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA705, AA
- the 7xxx series aluminum alloys used herein have an elemental composition as set forth in Table 1.
- the aluminum alloys used herein have an elemental composition as set forth in Table 2.
- the aluminum alloy includes zinc (Zn) in an amount of from 4% to 15% (e.g., from 5.4% to 9.5%, from 5.6% to 9.3%, from 5.8% to 9.2%, or from 4.0% to 5.0%) based on the total weight of the alloy.
- the aluminum alloy can include about 4.0%, about 4.1%, about 4.2%, about 4.3%, about 4.4 %, about 4.5%, about 4.6 %, about 4.7 %, about 4.8 %, about 4.9 %, about 5.0 %, about 5.1%, about 5.2 %, about 5.3%, about 5.4%, about 5.5%, about 5.6%, about 5.7%, about 5.8%, about 5.9%, about 6.0%, about 6.1%, about 6.2 %, about 6.3%, about 6.4%, about 6.5%, about 6.6%, about 6.7%, about 6.8%, about 6.9%, about 7.0%, about 7.1%, about 7.2%, about 7.3%, about 7.4%, about 7.5%, about 7.6%, about 7.7%, about 7.8%, about 7.9%, about 8.0%, about 8.1%, about 8.2%, about 8.3%, about 8.4%, about 8.5%, about 8.6%, about 8.7%, about 8.8%, about 8.9%, about 9.0%, about 9.1%, about 9.2%, about 9.3%, about 9.4%, about 9.5%, about 9.6%, about 9.7%, about
- the aluminum alloy includes copper (Cu) in an amount of from 0.1% to 3.5% (e.g., from 0.2% to 2.6%, from 0.3% to 2.5%, or from 0.15% to 0.6%) based on the total weight of the alloy.
- the aluminum alloy can include about 0.1%, about 0.11%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, about 0.20%, about 0.21%, about 0.22%, about 0.23%, about 0.24%, about 0.25%, about 0.26%, about 0.27%, about 0.28%, about 0.29%, about 0.30%, about 0.35%, about 0.40%, about 0.45%, about 0.50%, about 0.55%, about 0.60%, about 0.65%, about 0.70%, about 0.75%, about 0.80%, about 0.85%, about 0.90%, about 0.95%, about 1.0%, about 1.1%, about 1.2%, about 1.3%, about 1.4%, about 1.5%, about 1.6%, about 1.7%, about 1.8%, about 1.9%, about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3.0%
- the aluminum alloy includes magnesium (Mg) in an amount of from 1.0% to 4.0% (e.g., from 1.0% to 3.0%, from 1.4% to 2.8%, or from 1.6% to 2.6%).
- the aluminum alloy can include about 1.0%, about 1.1%, about 1.2%, about 1.3%, about 1.4%, about 1.5%, about 1.6%, about 1.7%, about 1.8%, about 1.9%, about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3.0%, about 3.1%, about 3.2%, about 3.3%, about 3.4%, about 3.5%, about 3.6%, about 3.7%, about 3.8%, about 3.9%, or about 4.0% Mg. All are expressed in wt. %.
- the aluminum alloy includes a combined content of Zn, Cu, and Mg ranging from about 5% to 14% (e.g., from 5.5% to 13.5%, from 6% to 13%, from 6.5% to 12.5%), or from 7% to 12%).
- the combined content of Zn, Cu, and Mg can be about 5.1%, about 5.5%, about 6.0%, about 6.5%, about 7.0%, about 7.5%, about 8.0%, about 8.5%, about 9.0%, about 9.5%, about 10.0%, about 10.5%, about 11.0%, about 11.5%, about 12.0%, about 12.5%, about 13.0%, about 13.5%, or about 14.0%. All are expressed in wt. %.
- the aluminum alloy includes iron (Fe) in an amount of from 0.05% to 0.50% (e.g., from 0.10% to 0.35% or from 0.10% to 0.25%) based on the total weight of the alloy.
- the aluminum alloy can include about 0.05%), about 0.06%), about 0.01%, about 0.08%, about 0.09%, about 0.10%, about 0.11%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, about 0.20%, about 0.21%, about 0.22%, about 0.23%, about 0.24%, about 0.25%, about 0.26%, about 0.27%, about 0.28%, about 0.29%, about 0.30%, about 0.31%, about 0.32%, about 0.33%, about 0.34%, about 0.35%, about 0.36%, about 0.37%, about 0.38%, about 0.39%, about 0.40%, about 0.41%,
- the aluminum alloy includes silicon (Si) in an amount of from 0.05% to 0.30% (e.g., from 0.05% to 0.25% or from 0.07% to 0.15%) based on the total weight of the alloy.
- the aluminum alloy can include about 0.05%>, about 0.06%, about 0.07%, about 0.08%, about 0.09%, about 0.10%, about 0.11%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, about 0.20%, about 0.21%, about 0.22%, about 0.23%, about 0.24%, about 0.25%, about 0.26%, about 0.27%, about 0.28%, about 0.29%, or about 0.30% Si. All are expressed in wt. %.
- the aluminum alloy includes zirconium (Zr) in amounts up to 0.50% (e.g., from 0.01% to 0.25%, from 0.03% to 0.20%, or from 0.05% to 0.15%) based on the total weight of the alloy.
- Zr zirconium
- the aluminum alloy can include about 0.01%, about 0.02%, about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, about 0.10%, about 0.11%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, about 0.20%, about 0.21%, about 0.22%, about 0.23%, about 0.24%, about 0.25%, about 0.26%, about 0.27%, about 0.28%, about 0.29%, about 0.30%, about 0.31%, about 0.32%, about 0.33%, about 0.34%, about 0.35%, about 0 36%, about 0.37%, about 0 38%, about 0.39%, about 0 40%, about 0.41%, about 0.42%, about 0.43%, about 0.44%, about 0.45%, about 0.46%, about 0.47%, about 0.48%), about 0.49%, or about 0.4
- the alloys can include Zr in an amount less than 0.05% (e.g., about 0.04%, about 0.03%, about 0.02%, or about 0 01%) based on the total weight of the alloy. In some cases, Zr is not present in the alloy (i.e., 0%>). All are expressed in wt. %.
- the aluminum alloy includes manganese (Mn) in an amount of up to 0.25% (e.g., from 0.01% to 0.10% or from 0.02% to 0.05%) based on the total weight of the alloy.
- the aluminum alloy can include about 0.01%, about 0.02%, about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, about 0.10%, about 0.1 1%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, about 0.20%, about 0.21%, about 0.22%, about 0.23%, about 0.24%, or about 0.25% Mn.
- Mn is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- the aluminum alloy includes chromium (Cr) in an amount of up to 0.20% (e.g., from 0.01% to 0.10%, from 0.01% to 0.05%, or from 0.03% to 0.05%) based on the total weight of the alloy.
- the aluminum alloy can include about 0.01%, about 0.02%, about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, about 0.10%, about 0.11%, about 0.12%, about 0.13%, about 0.14%, about 0.15%, about 0.16%, about 0.17%, about 0.18%, about 0.19%, or about 0.20% Cr.
- Cr is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- the aluminum alloy includes titanium (Ti) in an amount of up to 0.15% (e.g., from 0.001% to 0.10%, from 0.001% to 0.05%, or from 0.003% to 0.035%) based on the total weight of the alloy.
- the alloy can include about 0.001%, about 0.002%, about 0.003%, about 0.004%, about 0.005%, about 0.006%, about 0.007%, about 0.008%, about 0.009%, about 0.010%, about 0.01 1%, about 0.012%, about 0.013%, about 0.014%, about 0.015%, about 0.016%, about 0.017%, about 0.018%, about 0.019%, about 0.020%, about 0.021%, about 0.022%, about 0.023%, about 0.024%, about 0.025%, about 0.026%, about 0.027%, about 0.028%, about 0.029%, about 0.030%, about 0.031%, about 0.032%, about 0.033%, about 0.034%, about 0.035%, about 0.036%, about 0.037%, about 0.038%, about 0.039%, about 0.040%, about 0.041%, about 0.042%, about 0.043%, about 0.044%, about 0.045%, about 0.046%, about 0.047%, about 0.048%, about 0.049%, about 0.01%
- the aluminum alloy includes one or more elements selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu in an amount of up to 0.10% (e.g., from 0.01% to 0.10%, from 0.01% to 0.05%, or from 0.03% to 0.05%), based on the total weight of the alloy.
- the aluminum alloy can include about 0.01%, about 0.02%, about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, or about 0.10 % of one or more elements selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. All are expressed in wt. %.
- the aluminum alloy includes one or more elements selected from the group consisting of Mo, Nb, Be, B, Co, Sn, Sr, V, In, Hf, Ag, Sc, and Ni in an amount of up to 0.10% (e.g., from 0.01% to 0.10%, from 0.01% to 0.05%, or from 0.03% to 0.05%), based on the total weight of the alloy.
- the aluminum alloy can include about 0.01%, about 0.02%, about 0.03%, about 0.04%, about 0.05%, about 0.06%, about 0.07%, about 0.08%, about 0.09%, or about 0.10 % of one or more elements selected from the group consisting of Mo, Nb, Be, B, Co, Sn, Sr, V, In, Hf, Ag, Sc, and Ni. All are expressed in wt. %.
- the aluminum alloy includes other minor elements, sometimes referred to as impurities, in amounts of 0.15% or below, 0.14% or below, 0.13% or below, 0.12% or below, 0.1 1% or below, 0.10% or below, 0.09% or below, 0.08% or below, 0.07% or below, 0.06% or below, 0.05% or below, 0.04% or below, 0.03% or below, 0.02% or below, or 0.01% or below.
- these impurities include, but are not limited to, Ga, Ca, Bi, Na, Pb, or combinations thereof.
- one or more elements selected from the group consisting of Ga, Ca, Bi, Na, and Pb may be present in the aluminum alloy in amounts of 0.15% or below, 0.14% or below, 0.13% or below, 0.12% or below, 0.11% or below, 0.10% or below, 0.09% or below, 0.08% or below, 0.07% or below, 0.06% or below, 0.05% or below, 0.04% or below, 0.03% or below, 0.02% or below, or 0.01% or below.
- the sum of all impurities does not exceed 0.15% (e.g., 0.10%). All expressed in wt. %.
- the remaining percentage of the alloy is aluminum.
- the aluminum alloy products disclosed herein are able to resist hardening for up to about 6 months, and, during that time, exhibit desirable bendability and formability.
- 7xxx series aluminum alloy products prepared without the pre-aging step begin to age naturally within a few days of their production and quickly harden and become more difficult to bend and form.
- the aluminum alloy products disclosed herein exhibit stable and desirable strength and bendability following solutionizing.
- the aluminum alloy products disclosed herein can be easily formed at a temperature as low as those in the range of about 200 °C to 250 °C for up to about six months following their production.
- the aluminum alloy products are cold-formable at room temperature for up to six months following their production.
- the aluminum alloy products disclosed herein can have any suitable shape or physical configuration.
- the aluminum alloy products are rolled aluminum alloy products, which are formed by reducing the thickness of the material using a series of rollers. Such rolling can be carried out by hot rolling, cold rolling, or any combination thereof.
- the rolled aluminum alloy product is an aluminum alloy sheet or an aluminum alloy shate.
- Such shates or sheets can have a thickness of no more than 15 mm, no more than 14 mm, no more than 13 mm, no more than 12 mm, no more than 1 1 mm, no more than 10 mm, no more than 9 mm, no more than 8 mm, no more than 7 mm, no more than 6 mm, no more than 5 mm, no more than 4 mm, no more than 3 mm, no more than 2 mm, no more than 1 mm, no more than 0.5 mm, no more than 0.3 mm, or no more than 0.1 mm.
- the aluminum alloy product is a sheet
- such an aluminum alloy sheet has a yield strength (Rp), measured according to the ISO 6892-1 test, of at least 100 MPa, at least 120 MPa, at least 140 MPa, at least 160 MPa, at least 180 MPa, at least 200 MPa, at least 220 MPa, at least 240 MPa, at least 260 MPa, at least 280 MPa, at least 300 MPa, at least 320 MPa, at least 340 MPa, and up to about 360 MPa, up to about 380 MPa, or up to about 400 MPa, immediately following pre-aging.
- Rp yield strength
- such aluminum alloy sheets exhibit a "stable strength," which, for example, means that the yield strength (Rp), measured according to the ISO 6892-1 test, of the aluminum alloy sheet increases by no more than 25 MPa, no more than 20 MPa, no more than 15 MPa, no more than MPa, or no more than 5 MPa during a post-production period (i.e., the period immediately following the pre-aging).
- the post-production period generally ranges from about 7 days to about 180 days, from about 14 days to about 180 days, from about 21 days to about 180 days, from about 90 days to about 180 days, or from about 120 days to about 180 days.
- the post-production period is about 7 days, about 14 days, about 21 days, about 30 days, about 40 days, about 50 days, about 60 days, about 70 days, about 80 days, about 90 days, about 100 days, about 1 10 days, about 120 days, about 130 days, about 140 days, about 150 days, about 160 days, about 170 days, or about 180 days.
- the disclosed aluminum alloy products are the products of a disclosed method. Without intending to limit the scope of the inventions set forth herein, the properties of the aluminum alloy products set forth herein are partially determined by the formation of certain microstructures during the preparation thereof. In certain embodiments, the method of preparation can influence certain resulting properties in the aluminum alloy product.
- the aluminum alloy products disclosed herein can be prepared and processed by, for example, casting, homogenization, rolling, solutionizing, and quenching.
- the aluminum alloy products described herein can also be pre-aged.
- the methods disclosed herein comprise a step of casting a molten aluminum alloy to provide an aluminum alloy cast product.
- Such aluminum alloy cast products can be provided using any casting process.
- the alloys are cast using a direct chill (DC) casting process to provide a cast ingot.
- the alloys are cast using a continuous casting (CC) process that may include, but is not limited to, the use of twin-belt casters, twin-roll casters, or block casters.
- the casting process is performed by a CC process to provide a cast product in the form of a billet, a plate, a shate, a strip, and the like.
- the molten alloy may be treated before casting. The treatment can include one or more of degassing, inline fluxing, and filtering.
- the cast product can then be subjected to further processing steps, as described in further detail below.
- the processing steps can be used to prepare aluminum alloy sheets.
- the processing steps can be suitably applied to any cast product, including, but not limited to, ingots, billets, plates, strips, etc., using modifications and techniques as known to those of ordinary skill in the art.
- the homogenization step can include heating a cast aluminum alloy product prepared from an alloy composition described herein to attain a peak metal temperature (PMT) of at least 450 °C (e.g., at least 450 °C, at least 460 °C, at least 470 °C, at least 480 °C, at least 490 °C, at least 500 °C, at least 510 °C, at least 520 °C, at least 530 °C, at least 540 °C, at least 550 °C, at least 560 °C, at least 570 °C, or at least 580 °C).
- PMT peak metal temperature
- the cast aluminum alloy product can be heated to a temperature of from 460 °C to 640 °C, from 480 °C to 620 °C, from 500 °C to 600 °C, from 520 °C to 580 °C, from 530 °C to 575 °C, from 535 °C to 570 °C, from 540 °C to 565 °C, from 545 °C to 560 °C, from 530 °C to 560 °C, or from 550 °C to 580 °C.
- the heating rate to the PMT is 100 °C/hour or less, 75 °C/hour or less, 50 °C/hour or less, 40 °C/hour or less, 30 °C/hour or less, 25 °C/hour or less, 20 °C/hour or less, or 15 °C/hour or less.
- the heating rate to the PMT is from 10 °C/min to 100 °C/min (e.g., from 10 °C/min to 90 °C/min, from 10 °C/min to 70 °C/min, from 10 °C/min to 60 °C/min, from 20 °C/min to 90 °C/min, from 30 °C/min to 80 °C/min, from 40 °C/min to 70 °C/min, or from 50 °C/min to 60 °C/min).
- 10 °C/min to 90 °C/min e.g., from 10 °C/min to 70 °C/min, from 10 °C/min to 60 °C/min, from 20 °C/min to 90 °C/min, from 30 °C/min to 80 °C/min, from 40 °C/min to 70 °C/min, or from 50 °C/min to 60 °C/min.
- the cast aluminum alloy product is then allowed to soak (i.e., held at the indicated temperature) for a period of time.
- the cast aluminum alloy product is allowed to soak for up to 24 hours (e.g., from 30 minutes to 6 hours, inclusively).
- the cast aluminum alloy product is soaked at a temperature of at least 450 °C for about 30 minutes, for about 1 hour, for about 2 hours, for about 3 hours, for about 4 hours, for about 5 hours, for about 6 hours, for about 7 hours, for about 8 hours, for about 9 hours, for about 10 hours, for about 11 hours, for about 12 hours, for about 13 hours, for about 14 hours, for about 15 hours, for about 16 hours, for about 17 hours, for about 18 hours, for about 19 hours, for about 20 hours, for about 21 hours, for about 22 hours, for about 23 hours, for about 24 hours, or for any time period in between.
- the cast aluminum alloy product is allowed to cool to room temperature in the air.
- one or more hot rolling passes are performed.
- the aluminum alloy products are laid down and hot rolled at a temperature ranging from about 250 °C to about 550 °C (e.g., from about 300 °C to about 500 °C or from about 350 °C to about 450 °C).
- the aluminum alloy product is hot rolled to an about 4 mm to about 15 mm gauge (e.g., from 5 mm to 12 mm gauge).
- the aluminum alloy product can be hot rolled to an about 15 mm gauge, an about 14 mm gauge, an about 13 mm gauge, an about 12 mm gauge, an about 11 mm gauge, an about 10 mm gauge, an about 9 mm gauge, an about 8 mm gauge, an about 7 mm gauge, an about 6 mm gauge, or an about 5 mm gauge.
- the aluminum alloy product can be hot rolled to a gauge no more than 4 mm (i.e., a sheet).
- the aluminum alloy product is hot rolled to an about 1 mm to an about 4 mm gauge.
- the aluminum alloy product can be hot rolled to an about 4 mm gauge, an about 3 mm gauge, an about 2 mm gauge, or an about 1 mm gauge.
- the rolled product from the hot rolling step can be cold rolled to a thin gauge shate or sheet.
- this thin-gauge shate or sheet is cold rolled to have a thickness up to 12.0 mm, such as a thickness ranging from about 1.0 mm to about 12.0 mm, from about 2.0 mm to about 8.0 mm, from about 3.0 mm to about 6.0 mm, or from about 4.0 mm to about 5.0 mm.
- this thin- gauge shate or sheet is cold rolled to have a thickness of about 12.0 mm, about 11.9 mm, about 11.8 mm, about 11.7 mm, about 11.6 mm, about 11.5 mm, about 11.4 mm, about 1 1.3 mm, about 1 1.2 mm, about 11.1 mm, about 11.0 mm, about 10.9 mm, about 10.8 mm, about 10.7 mm, about 10.6 mm, about 10.5 mm, about 10.4 mm, about 10.3 mm, about 10.2 mm, about 10.1 mm, about 10.0 mm, about 9.9 mm, about 9.8 mm, about 9.7 mm, about 9.6 mm, about
- the solutionizing step can include heating the sheet, plate, or shate from room temperature to a temperature of from 430 °C to 510 °C (e.g., from 440 °C to 500 °C, from 450 °C to 490 °C, from 460 °C to 480 °C).
- the sheet, plate, or shate can soak at the temperature for a period of time.
- the alloy is allowed to soak for up to approximately 5 minutes (e.g., from 5 seconds to 5 minutes, inclusively).
- the sheet, plate, or shate can soak at the temperature of from 430 °C to 510 °C for about 5 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 25 seconds, about 30 seconds, about 35 seconds, about 40 seconds, about 45 seconds, about 50 seconds, about 55 seconds, about 60 seconds, about 65 seconds, about 70 seconds, about 75 seconds, about 80 seconds, about 85 seconds, about 90 seconds, about 95 seconds, about 100 seconds, about 105 seconds, about 1 10 seconds, about 115 seconds, about 120 seconds, about 125 seconds, about 130 seconds, about 135 seconds, about 140 seconds, about 145 seconds, about 150 seconds, about 3 minutes, about 4 minutes, or about 5 minutes, or anywhere in between.
- the plate, shate, or sheet can then be cooled to a temperature of 25 °C to 65 °C at a quench speed that can vary between about 50 °C/s to about 400 °C/s in a quenching step that is based on the selected gauge.
- the quench rate can be from about 50 °C/s to about 375 °C/s, from about 60 °C/s to about 375 °C/s, from about 70 °C/s to about 350 °C/s, from about 80 °C/s to about 325 °C/s, from about 90 °C/s to about 300 °C/s, from about 100 °C/s to about 275 °C/s, from about 125 °C/s to about 250 °C/s, from about 150 °C/s to about 225 °C/s, or from about 175 °C/s to about 200 °C/s.
- the sheet, plate, or shate is rapidly quenched with a liquid (e.g., water) and/or gas or another selected quench medium.
- a liquid e.g., water
- gas or another selected quench medium e.g., water
- the sheet, plate, or shate can be rapidly quenched with water.
- the sheet, plate, or shate is quenched with a gas or a liquid.
- the methods disclosed herein generally include a pre-aging step following the solutionizing and quenching steps.
- the pre-aging step can include heating the alloy after the solutionizing step to a temperature ranging from about 60 °C to about 130 °C (e.g., from about 65 °C to about 125 °C, from about 70 °C to about 120 °C, from about 75 °C to about 1 15 °C, from about 80 °C to about 120 °C, or from about 85 °C to about 1 15 °C).
- the pre-aging step can include heating the alloy after solutionizing from about 80 °C to about 120 °C (e.g., from about 90 °C to about 110 °C).
- the pre-aging step may be conducted for a period of time up to approximately 24 hours (e.g., for a period of time up to about 20 hours, up to about 15 hours, up to about 12 hours, up to about 10 hours, up to about 9 hours, up to about 8 hours, up to about 7 hours, up to about 6 hours, up to about 5 hours, up to about 4 hours, up to about 3 hours, up to about 2 hours, up to about 1 hours, or up to about 30 minutes).
- the alloy can soak at the temperature for a period of time.
- the alloy is allowed to soak for a period of time up to approximately 2 hours (e.g., for a period of time up to about 1 minute, up to about 2 minutes, up to about 3 minutes, up to about 4 minutes, up to about 5 minutes, up to about 6 minutes, up to about 7 minutes, up to about 8 minutes, up to about 9 minutes, up to about 10 minutes, up to about 20 minutes, up to about 30 minutes, up to about 40 minutes, up to about 45 minutes, up to 6 about 0 minutes, or up to about 90 minutes).
- the time between the post-solutionizing quench and the pre-aging can be any length of time ranging from about 0 minutes up to about 60 minutes.
- the time between the post-solutionizing quench and the pre-aging can be any length of time ranging from about 5 minutes up to about 45 minutes or from about 10 minutes up to about 35 minutes.
- the heated product is generally cooled from the peak pre-aging temperature back to room temperature slowly and without the use of quenching the product with a gas or a liquid.
- the cooling to room temperature is assisted by forced cooling using, for example, air, a cool liquid, and the like, or any combination thereof.
- the cooling from the peak pre-aging temperature back to room temperature occurs over the course of about 48 hours, about 36 hours, about 24 hours, about 18 hours, about 12 hours, or for any range of time in between.
- the aluminum alloy product can be cooled from the pre-aging temperature to room temperature in any suitable physical configuration.
- the aluminum alloy product is coiled at the pre-aging temperature (or at a temperature no more than 5 °C below the pre-aging temperature), and cooled to room temperature over the course of about 48 hours, about 36 hours, about 24 hours, about 18 hours, about 12 hours, or for any range of time in between.
- the aluminum alloy product is in a form that is ready for delivery, and suitable for use in various cold forming and warm forming processes.
- the aluminum alloy product in a stable T4 temper, which is retained for a period of up to about 6 months, after which point the formed material ages and hardens.
- the disclosure provides an article of manufacture, which is comprised of a 7xxx series aluminum alloy product disclosed herein.
- the article of manufacture comprises a rolled aluminum alloy product, such as a rolled aluminum alloy sheet.
- articles of manufacture include, but are not limited to, an automobile, a truck, a trailer, a train, a railroad car, an airplane, a body panel or part for any of the foregoing, a bridge, a pipeline, a pipe, a tubing, a boat, a ship, a storage container, a storage tank, a an article of furniture, a window, a door, a railing, a functional or decorative architectural piece, a pipe railing, an electrical component, a conduit, a beverage container, or a food container.
- the aluminum alloy products disclosed herein can be used in automotive and/or transportation applications, including motor vehicle, aircraft, and railway applications, or any other desired application.
- the aluminum alloy products disclosed herein can be used to prepare motor vehicle body part products, such as bumpers, side beams, roof beams, cross beams, pillar reinforcements (e.g., A-pillars, B-pillars, and C-pillars), inner panels, outer panels, side panels, inner hoods, outer hoods, or trunk lid panels.
- the aluminum alloys and methods described herein can also be used in aircraft or railway vehicle applications, to prepare, for example, external and internal panels.
- the aluminum alloy products disclosed herein can be used in electronics applications.
- the aluminum alloy products disclosed herein can also be used to prepare housings for electronic devices, including mobile phones and tablet computers.
- the alloys can be used to prepare housings for the outer casing of mobile phones (e.g., smart phones) and tablet bottom chassis.
- the aluminum alloy products disclosed herein can be used in industrial applications.
- the aluminum alloy products disclosed herein can be used to prepare products for the general distribution market.
- the aluminum alloy products disclosed herein can be used as aerospace body parts.
- the aluminum alloy products disclosed herein can be used to prepare structural aerospace body parts, such as a wing, a fuselage, an aileron, a rudder, an elevator, a cowling, or a support.
- the aluminum alloy products disclosed herein can be used to prepare non-structural aerospace body parts, such as a seat track, a seat frame, a panel, or a hinge.
- any reference to a series of embodiments is to be understood as a reference to each of those examples disjunctively (e.g., "Embodiments 1-4" is to be understood as “Embodiments 1, 2, 3, or 4").
- Embodiment 1 is a method of making a rolled aluminum alloy product, comprising: providing a 7xxx series aluminum alloy, wherein the 7xxx series aluminum alloy is provided as a molten 7xxx series aluminum alloy; casting the molten 7xxx series aluminum alloy to provide an aluminum alloy cast product; homogenizing the aluminum alloy cast product to provide a homogenized aluminum alloy cast product; rolling the homogenized aluminum alloy cast product to form a rolled aluminum alloy product; and solutionizing and pre-aging the rolled aluminum alloy product.
- Embodiment 2 is the method of Embodiment 1, wherein the 7xxx series aluminum alloy is selected from the group consisting of AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA701 1, AA7012, AA7014, AA7016, AA71 16, AA7122, AA7023, AA7026, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036,
- Embodiment 3 is the method of any of Embodiments 1-2, wherein the 7xxx series aluminum alloy comprises: from 4.0 to 15.0 wt. % Zn; from 0.1 to 3.5 wt % Cu; from 1.0 to 4.0 wt. % Mg; from 0.05 to 0.50 wt. % Fe; from 0.05 to 0.30 wt. % Si; up to 0.50 wt. % Zr; up to 0.25 wt. % Mn; up to 0.20 wt. % Cr; up to 0.15 wt. % Ti; and up to 0.15 wt. % impurities; with the remainder being Al.
- Embodiment 4 is the method of any of Embodiments 1-3, wherein the 7xxx series aluminum alloy comprises: from 5.6 to 9.3 wt. % Zn; from 0.2 to 2.6 wt. % Cu; from 1.4 to 2.8 wt. % Mg; from 0.10 to 0.35 wt. % Fe; from 0.05 to 0.20 wt. % Si; up to 0.25 wt. % Zr; up to 0.05 wt. % Mn; up to 0.05 wt. % Cr; up to 0.05 wt. % Ti; and up to 0.15 wt. % impurities; with the remainder being Al.
- Embodiment 5 is the method of Embodiment 3, further comprising up to 0.10 wt. % of one or more elements selected from the group consisting of Mo, b, Be, B, Co, Sn, Sr, V, In, Hf, Ag, Sc, Ni, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- Embodiment 6 is the method of any of Embodiments 1-5, wherein the rolled aluminum alloy product is an aluminum alloy sheet or an aluminum alloy shate.
- Embodiment 7 is the method of Embodiment 6, wherein the rolled aluminum alloy product has a thickness of no more than 15 mm.
- Embodiment 8 is the method of any of Embodiments 1-7, wherein the casting comprises direct chill (DC) casting or continuous casting.
- DC direct chill
- Embodiment 9 is the method of any of Embodiments 1-8, wherein the rolling comprises hot rolling, cold rolling, or any combination thereof.
- Embodiment 10 is the method of any of Embodiments 1-9, further comprising quenching the rolled aluminum alloy product after the solutionizing and preceding the pre- aging.
- Embodiment 11 is the method of any of Embodiments 1-10, wherein the pre-aging comprises heating the rolled aluminum alloy product to a temperature ranging from 60 °C to 130 °C.
- Embodiment 12 is the method of any of Embodiments 1-1 1, wherein the pre-aging is conducted for a period of time up to about 24 hours.
- Embodiment 13 is the method of any of Embodiments 1-12, further comprising, after the pre-aging, cooling the rolled aluminum alloy product to about room temperature over a period of time ranging from 12 hours to 48 hours.
- Embodiment 14 is the method of any of Embodiments 1-13, further comprising, after the pre-aging, coiling the rolled aluminum alloy product, and, then, cooling the rolled aluminum alloy product to room temperature.
- Embodiment 15 is the method of Embodiment 14, wherein the coiling is carried out at a temperature of no more than 5 °C below the temperature of the pre-aging.
- Embodiment 16 is the method of Embodiment 15, wherein the cooling is carried out over a period of time ranging from 12 hours to 48 hours.
- Embodiment 17 is the method of any of Embodiments 1-16, further comprising coiling the rolled aluminum alloy product after the pre-aging.
- Embodiment 18 is the method of any of Embodiments 1-17, wherein the rolled aluminum alloy product has a yield strength (R p ) of at least 240 MPa immediately following pre-aging, wherein the yield strength (R p ) is measured according to ISO 6892-1.
- Embodiment 19 is the method of any of Embodiments 1-18, wherein the rolled aluminum alloy product exhibits an increase in its yield strength (R p ) of no more than 25 MPa during a post-production period immediately following the pre-aging, wherein the post- production period ranges from 7 days to 180 days.
- R p yield strength
- Embodiment 20 is an aluminum alloy product, wherein the aluminum alloy product is a rolled aluminum alloy product made by a method of any of Embodiments 1-19.
- FIG. 1 shows the change in the yield strength (Rp) as a function of the number of days following initial production for each of the samples, where the yield strength is measured according to the ISO 6892-1 test.
- the sample prepared with pre- aging shows a significantly more stable yield strength over a period of about 30 days.
- FIG. 2 shows the change in the yield strength (Rp) as a function of the number of days following initial production for each of the samples.
- Samples of AA7075 aluminum alloy sheets of 1.4 mm thickness were prepared according to identical processing methods, including solutionizing at 480 °C with a five minute soak time, a full water quench at a quench rate of 350 °C/s, a pre-aging step, and natural aging.
- the pre-aging temperature and time were varied, as was the natural aging time.
- the pre-aging time was either 1 hours, 4 hours, or 8 hours.
- the pre-aging temperature was either 70 °C or 100 °C.
- Natural aging (NA) was conducted for 1 week, 2 weeks, 3 weeks, or 4 weeks. The samples were tested with and without being subjected to a paint-bake cycle (PB).
- FIGS. 3A-D show the change in the yield strength for the sample as a function of the pre-aging time and temperature and as a function of whether the samples were subjected to a paint-bake cycle.
- FIG 3D shows the effect of pre-strain when the samples were subjected to paint-baking.
- the yield strength (MPa) was measured according to the ISO 6892-1 :2016 test.
- FIGS. 4A-C show the change in elongation strength for the sample as a function of the pre-aging time and temperature and as a function of whether the samples were subjected to a paint-bake cycle.
- FIG 4D shows the effect of pre-strain when the samples were subjected to paint-baking.
- the elongation strength (MPa) was measured according to the ISO 6892-1 :2016 test.
- FIGS. 5A-C show the change in uniform elongation for the sample as a function of the pre-aging time and temperature and as a function of whether the samples were subjected to a paint-bake cycle.
- FIG 5D shows the effect of pre-strain when the samples were subjected to paint-baking.
- the uniform elongation (%) was measured according to the ISO 6892-1 :2016 test.
- FIGS. 7A-D show the change in critical fracture strain for the sample as a function of the pre-aging time and temperature and as a function of whether the samples were subjected to a paint-bake cycle.
- FIGS 7C and D show the effect of pre-strain when the samples were subjected to paint-baking.
- the critical fracture strain (%) was measured according to the ISO 6892-1 :2016 test.
- FIGS. 8A-D show the strain hardening exponent (n-value) for the sample as a function of the pre-aging time and temperature and as a function of whether the samples were subjected to a paint-bake cycle.
- FIGS 8C and D show the effect of pre-strain when the samples were subjected to paint-baking.
- the critical fracture strain (%) was measured according to the ISO 6892-1 :2016 test. [0099] As shown by FIGS. 3-8, pre-aging at 70 °C resulted in increasing yield strength as the length of natural aging increased.
- yield strength was relatively stable when pre-aged for 4 to 8 hours, regardless of the length of time of natural aging. Yield strengths of greater than 450 MPa were achievable after the samples were subjected to a paint- bake cycle. The samples subjected to a 2% pre-strain prior to the paint-bake cycle showed a slight increase in yield strength.
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Abstract
Priority Applications (7)
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KR1020207008466A KR20200047598A (ko) | 2017-08-29 | 2018-08-28 | 안정된 t4 템퍼의 7xxx 시리즈 알루미늄 합금 제품 및 이를 제조하는 방법 |
JP2020508462A JP6971380B2 (ja) | 2017-08-29 | 2018-08-28 | 安定したt4調質での7xxxシリーズのアルミニウム合金製品およびその作製方法 |
KR1020227030142A KR102647056B1 (ko) | 2017-08-29 | 2018-08-28 | 안정된 t4 템퍼의 7xxx 시리즈 알루미늄 합금 제품 및 이를 제조하는 방법 |
MX2020001995A MX2020001995A (es) | 2017-08-29 | 2018-08-28 | Productos de aleacion de aluminio serie 7xxx en un temple t4 estable y metodos para la fabricacion de estos. |
CA3070003A CA3070003A1 (fr) | 2017-08-29 | 2018-08-28 | Produits en alliage d'aluminium de serie 7xxx dans un etat de revenu t4 stabilise et leurs procedes de fabrication |
CN201880056524.9A CN111183242A (zh) | 2017-08-29 | 2018-08-28 | 处于稳定t4回火的7xxx系列铝合金产品和其制造方法 |
EP18766496.6A EP3676412B1 (fr) | 2017-08-29 | 2018-08-28 | Produits en alliage d'aluminium de série 7xxx dans un état de revenu t4 stabilisé et leurs procédés de fabrication |
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- 2018-08-28 KR KR1020207008466A patent/KR20200047598A/ko active Application Filing
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CN111424197A (zh) * | 2020-04-14 | 2020-07-17 | 广西南南铝加工有限公司 | 一种航空用耐蚀铝合金及其制备方法 |
CN111424197B (zh) * | 2020-04-14 | 2021-12-21 | 广西南南铝加工有限公司 | 一种航空用耐蚀铝合金及其制备方法 |
Also Published As
Publication number | Publication date |
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EP3676412B1 (fr) | 2024-08-14 |
JP2020530882A (ja) | 2020-10-29 |
US20190062886A1 (en) | 2019-02-28 |
MX2020001995A (es) | 2020-03-24 |
EP3676412A1 (fr) | 2020-07-08 |
JP6971380B2 (ja) | 2021-12-01 |
CN111183242A (zh) | 2020-05-19 |
KR102647056B1 (ko) | 2024-03-14 |
KR20200047598A (ko) | 2020-05-07 |
KR20220125371A (ko) | 2022-09-14 |
CA3070003A1 (fr) | 2019-03-07 |
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