WO2024126341A1 - Produits corroyés 7xxx présentant un compromis amélioré des propriétés de traction et de ténacité et procédé de production - Google Patents

Produits corroyés 7xxx présentant un compromis amélioré des propriétés de traction et de ténacité et procédé de production Download PDF

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WO2024126341A1
WO2024126341A1 PCT/EP2023/085062 EP2023085062W WO2024126341A1 WO 2024126341 A1 WO2024126341 A1 WO 2024126341A1 EP 2023085062 W EP2023085062 W EP 2023085062W WO 2024126341 A1 WO2024126341 A1 WO 2024126341A1
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product according
weight
hours
content
manufacture
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PCT/EP2023/085062
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English (en)
Inventor
Ricky WHELCHEL
Michael M NIEDZINSKI
Kenneth Paul Smith
Timothy Warner
Jean-Christophe Ehrstrom
Armelle Danielou
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Constellium Rolled Products Ravenswood, Llc
Constellium Issoire
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Priority claimed from EP22213912.3A external-priority patent/EP4386097A1/fr
Application filed by Constellium Rolled Products Ravenswood, Llc, Constellium Issoire filed Critical Constellium Rolled Products Ravenswood, Llc
Publication of WO2024126341A1 publication Critical patent/WO2024126341A1/fr

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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
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent

Definitions

  • the present disclosure relates to a method for manufacturing 7xxx aluminum wrought product with improved compromise of tensile and toughness properties and excellent cryogenic properties and fatigue resistance in corrosive environment and more particularly to such manufacturing processes and rolled products and use, notably designed for aeronautical and aerospace engineering and applications at cryogenic temperatures.
  • High strength 7xxx aluminum alloy products also designated as Al-Zn-Mg-Cu type alloy products, are extensively used in aerospace structure application, in which the material strength, fracture toughness, fatigue resistance, and corrosion resistance are required simultaneously. It is known that these various required properties cannot all be optimized at the same time and independently of each other during the fabrication of semi-finished products and structural elements for aeronautical construction.
  • chemical composition of the alloy or the parameters of product manufacturing processes are modified, several critical properties may tend to change in opposing directions. This is sometimes the case firstly for properties generally referred to as "static mechanical strength” (particularly the ultimate tensile stress UTS and the tensile yield stress TYS), and secondly for properties generally names as "damage tolerance" (particularly the toughness and the resistance to crack propagation).
  • Al-Zn-Mg-Cu alloys with high fracture toughness and high mechanical strength are described in the prior art.
  • US Patent 5,312,498 discloses a method of producing an aluminum-based alloy product having improved exfoliation resistance and fracture toughness which comprises providing an aluminum-based alloy composition consisting essentially of about 5.5- 10.0% by weight of zinc, about 1.75-2.6% by weight of magnesium, about 1.8-2.75% by weight of copper with the balance aluminum and other elements.
  • the aluminum-based alloy is worked, heat treated, quenched and aged to produce a product having improved corrosion resistance and mechanical properties.
  • US Patent 5,560,789 describes AA 7000 series alloys having high mechanical strength and a process for obtaining them.
  • the alloys contain, by weight, 7 to 13.5% Zn, 1 to 3.8% Mg, 0.6 to 2.7% Cu, 0 to 0.5% Mn, 0 to 0.4% Cr, 0 to 0.2% Zr, others up to 0.05% each and 0.15% total, and remainder Al.
  • US Patent No 5,865,911 describes an aluminum alloy consisting essentially of (in weight %) about 5.9 to 6.7% zinc, 1.8 to 2.4% copper, 1.6 to 1.86% magnesium, 0.08 to 0.15% zirconium balance aluminum and incidental elements and impurities.
  • the '911 patent particularly mentions the compromise between static mechanical strength and toughness.
  • US Patent No 6,027,582 describes a rolled, forged or extruded Al-Zn-Mg-Cu aluminum base alloy products greater than 60 mm thick with a composition of (in weight %), Zn: 5.7-8.7, Mg: 1.7-2.5, Cu: 1.2-2.2, Fe: 0.07-0.14, Zr: 0.05-0.15 with Cu + Mg ⁇ 4.1 and Mg>Cu.
  • US Patent No 6,972,110 teaches an alloy, which contains preferably (in weight %) Zn: 7-9.5, Mg: 1.3-1.68 and Cu 1.3-1.9 and encourages keeping Mg +Cu ⁇ 3.5.
  • PCT Patent Application No W02004090183 discloses an 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 aluminum, wherein (in weight percent): 0.1 [Cu] + 1.3 ⁇ [Mg] ⁇ 0.2[Cu] + 2.15, preferably 0.2[Cu] + 1.3 ⁇ [Mg] ⁇ 0.1[Cu] + 2.15.
  • US 20050006010 discloses a method for producing a high strength Al-Zn- Cu-Mg alloy with an improved fatigue crack growth resistance and a high damage tolerance, comprising the steps of casting an ingot with the following composition (in weight percent) Zn 5.5-9.5, Cu 1.5-3.5, Mg 1.5-3.5, Mn ⁇ 0.25, Zr ⁇ 0.25, Cr ⁇ 0.10, Fe ⁇ 0.25, Si ⁇ 0.25, Ti ⁇ 0.10, Hf and/or V ⁇ 0.25, other elements each less than 0.05 and less than 0.15 in total, balance aluminum, homogenizing and/or preheating the ingot after casting, hot working the ingot and optionally cold working into a worked product of more than 50 mm thickness, solution heat treating, quenching the heat treated product, and artificially aging the worked and heat-treated product, wherein the aging step comprises a first heat treatment at a temperature in a range of 105 ° C.
  • EP 1544315 discloses a product, especially rolled, extruded or forged, made of an AIZnCuMg alloy with constituents having the following percentage weights: Zn 6.7 - 7.3; Cu 1.9 - 2.5; Mg 1.0 - 2.0; Zr 0.07 - 0.13; Fe less than 0.15; Si less than 0.15; other elements not more than 0.05 to at most 0.15 per cent in total; and aluminum the remainder, wherein Mg/Cu ⁇ l.
  • the product is preferably treated by solution heat treatment, quenching, cold working and artificial aging.
  • US Patent No 8,277,580 teaches a rolled or forged Al-Zn-Cu-Mg aluminum-based alloy wrought product having a thickness from 2 to 10 inches.
  • the product has been treated by solution heattreatment, quenching and aging, and the product comprises (in weight- %): Zn 6.2-7.2, Mg 1.5- 2.4, Cu 1.7-2.1.
  • Fe 0-0.13, Si 0-0.10, Ti 0-0.06, Zr 0.06-0.13, Cr 0-0.04, Mn 0-0.04, impurities and other incidental elements ⁇ 0.05 each.
  • US Patent No 8,673,209 discloses aluminum alloy products about 4 inches thick or less that possesses the ability to achieve, when solution heat treated, quenched, and artificially aged, and in parts made from the products, an improved combination of strength, fracture toughness and corrosion resistance, the alloy consisting essentially of: about 6.8 to about 8.5 wt. % Zn, about 1.5 to about 2.00 wt. % Mg, about 1.75 to about 2.3 wt. % Cu; about 0.05 to about 0.3 wt. % Zr, less than about 0.1 wt. % Mn, less than about 0.05 wt. % Cr, the balance Al, incidental elements and impurities and a method for making same.
  • W02019/007817 concerns an extruded, rolled and/or forged aluminum-based alloy product having a thickness of at least 25 mm comprising (in weight %): Zn 6.70 -7.40; Mg 1.50 -1.80; Cu 2.20 -2.60, with a Cu to Mg ratio of at least 1.30; Zr 0.04 -0.14; M n 0 -0.5; Ti 0 -0.15; V 0 -0.15; Cr 0 -0.25; Fe 0 -0.15; Si 0 -0.15; impurities ⁇ 0.05 each and ⁇ 0.15 total.
  • EP2322677 discloses aluminum alloy products, such as plate, forgings and extrusions, suitable for use in making aerospace structural components like integral wing spars, ribs and webs, comprises about: 6 to 10 wt. % Zn; 1.2 to 1.9 wt. % Mg; 1.2 to 2.2 wt. % Cu, with Mg ⁇ (Cu + 0.3); and 0.05 to 0.4 wt. % Zr, the balance Al, incidental elements and impurities.
  • the alloy contains about 6.9 to 8.5 wt. % Zn; 1.2 to 1.7 wt. % Mg; 1.3 to 2 wt. % Cu.
  • This alloy provides improved combinations of strength and fracture toughness in thick gauges. When artificially aged per the three stages method of preferred embodiments, this alloy also achieves superior SCC performance, including under seacoast conditions.
  • the present invention relates to a method for manufacturing a high strength 7xxx aluminum wrought products by controlling the composition, in particular the quantity of Fe and Si and the fabrication parameters, in particular artificial aging conditions, to provide improved compromise between tensile yield strength and toughness with improved cryogenic fracture toughness, and fatigue resistance in corrosive environment.
  • the invention also concerns a rolled 7xxx product which can be obtained by the method of the invention.
  • cryogenic temperature is defined in accordance with the present invention to include temperatures significantly below room temperature and typically below - 100°C (173 K). Thus, the temperatures at which hydrogen (-253°C/20 K), oxygen (-183°C/90 K) and nitrogen (- 196°C/77 K) become liquid at atmospheric pressure are included as cryogenic temperatures. For purposes of experimental evaluation, a temperature of -196°C/77K is considered as a cryogenic temperature.
  • Room temperature is defined in accordance with its common usage and includes temperatures from about 20°C to about 25°C. For purposes of experimental evaluation, a temperature of 22°C is considered to be room temperature.
  • the present invention is directed to a process for the manufacture of a wrought 7xxx aluminum- based alloy product comprising the steps of: a) preparing a bath of molten alloy metal comprising in weight-% (wt. %)
  • Ti 0 - 0.15 preferably from 0.02 to 0.06 wt. %
  • the process is advantageously made with a bath of molten alloy wherein Zn content is in weight % (wt. %) from 6.90 to 7.30, even more preferably from 6.90 to 7.25.
  • the process is advantageously made with a bath of molten alloy wherein Cu content is in weight % (wt. %) from 1.95 to 2.35, even more preferably from 2.00 to 2.35.
  • said bath of molten alloy metal comprises in weight % (wt. %) Zn 6.90 - 7.30, Mg 1.35 - 1.75, Cu 1.95 - 2.35, Zr 0.04 - 0.14, Mn 0 - 0.5, Ti 0 - 0.15, V 0 - 0.15, Cr 0 - 0.25, Fe ⁇ 0.05, Si ⁇ 0.05% with a Fe+Si ⁇ 0.08 % and other impurities ⁇ 0.05 each and ⁇ 0.15 total, remainder aluminum.
  • said bath of molten alloy metal comprises in weight % (wt.
  • the process is advantageously made with a bath of molten alloy comprising Si ⁇ 0.03 wt. % and Fe ⁇ 0.05 wt. %.
  • the sum Fe+Si content is ⁇ 0.07 wt. %, even more preferably ⁇ 0.06 wt. %.
  • the sum Fe+Si content is > 0.03 wt. %, even more preferably > 0.04 wt. %.
  • the present invention is directed to a rolled product with a thickness t in millimeter of at least
  • the composition of the rolled product comprises a Zn content in weight % (wt. %) from 6.90 to 7.30, even more preferably from 6.90 to 7.25.
  • the composition of the rolled product comprises a Cu content is in weight % (wt. %) from 1.95 to 2.35, even more preferably from 2.00 to 2.35.
  • the composition of the rolled product comprises in weight % (wt. %) Zn 6.90 - 7.30, Mg 1.35 - 1.75, Cu 1.95 - 2.35, Zr 0.04 - 0.14, Mn 0 - 0.5, Ti 0 - 0.15, V 0 - 0.15, Cr 0 - 0.25, Fe ⁇ 0.05, Si ⁇ 0.05% with a Fe+Si ⁇ 0.08 % and other impurities ⁇ 0.05 each and ⁇ 0.15 total, remainder aluminum. More preferably, the composition of the rolled product comprises in weight % (wt.
  • the rolled product according to the invention displays a surprising small drop in both fracture toughness and elongation from room temperature down to liquid nitrogen temperature.
  • the rolled product according to the invention displays a toughness Klc(T- L) in MPa. ⁇ /m, at cryogenic temperature of about -196°C, measured according to ASTM standard E399 2020 which is reduced by less than 10 %, preferably by less than 8%, more preferably by less than 7 % in comparison with Klc(T-L) in MPa. ⁇ /m, measured at room temperature according to ASTM standard E399 -2020.
  • the rolled product according to the invention displays a toughness Klc(T-L) in MPa.Vm, at cryogenic temperature of about -196°C, measured according to ASTM standard E399 -2020, higher than -0.15*t +45 MPa.Vm , preferably higher than - 0.15*t+49 MPa.Vm, even more preferably higher than -0.15*t+55 MPa, where t is the thickness of the rolled product in mm.
  • the rolled product has a thickness from 70 mm to 160 mm, preferably from 70 mm to 102 mm.
  • the rolled product comprises Si ⁇ 0.03 wt. % and Fe ⁇ 0.05 wt. %.
  • the rolled product comprises a sum of Fe+Si content which is ⁇ 0.07 wt. %, even more preferably ⁇ 0.06 wt. %.
  • the rolled product comprises a sum of Fe+Si content which is > 0.03 wt. %, even more preferably > 0.04 wt. %.
  • the rolled product comprises a sum of Fe+Si content which is from 0.03 wt. % to 0.08 wt. %, preferably from 0.03 wt. % to 0.07 wt. %, even more preferably from .03 wt. % to 0.06 wt. %.
  • the rolled product comprises a Zn content in weight from 7.10 to 7.25 wt.%.
  • the rolled product comprises a Ti content in weight % (wt. %) which is ⁇ 0.06, preferably from 0.02 to 0.06, even more preferably from 0.03 to 0.05.
  • the rolled product according to the present invention or the product obtained by the process according to the invention is advantageously used as or incorporated in structural members for the construction of aircraft or spacecraft. It can be used as wing ribs, spars and/or frames.
  • the rolled product according to the present invention or the product obtained by the process according to the invention is advantageously used to manufacture a mechanical part, such as piston, impeller, for gas compression at cryogenic temperature below -100°C, in particular for hydrogen or oxygen or nitrogen or methane or natural gas compression.
  • the rolled product according to the present invention or the product obtained by the process according to the invention is advantageously used to manufacture a cryogenic tank or a stationary inland storage tank or a transportation storage tank of liquid gas such liquid hydrogen or liquid oxygen or liquid nitrogen or liquid methane or liquid natural gas.
  • Figure 1 shows the evolution of toughness Ki c (T-L) at cryogenic temperature versus the thickness of the plate.
  • Figure 2 shows the compromise at Room temperature (RT) between tensile yield strength in the rolling direction (L) and the toughness in L-T, measured at mid thickness.
  • Figure 3 shows the evolution of the compromise TYS in the rolling direction and toughness Ki c (T-L) at room temperature and cryogenic temperature.
  • Figure 4 shows the evolution of toughness Ki c (L-T) at Room temperature versus the sum Fe +Si for different compositions.
  • Figure 5 shows the evolution of toughness Ki c (L-T) at Room temperature versus the sum Fe +Si for different artificial aging conditions
  • Figure 6 shows the evolution of toughness Ki c (L-T) versus the thickness of the plate.
  • Figure 7 shows the fatigue crack growth rate (L-T) for a reference product in normal ambient air humidity condition and humid air condition.
  • Figure 8 shows the fatigue crack growth rate (L-T) for a product according to the invention in normal ambient air humidity condition and humid air condition.
  • tempers are laid down in NF EN 515 (2017).
  • static mechanical characteristics i.e., the ultimate tensile strength UTS, the tensile yield stress TYS and the elongation at fracture E, are determined by a tensile test according to standard ASTM B557, the location at which the pieces are taken and their direction being defined in ASTM B557.
  • standard EN 12258 apply.
  • the fracture toughness Kic is determined according to ASTM standard E399-2020. Materials are tested at t/2 up to 102 mm (4 inch) thickness, and t/4 for thicknesses greater than 102 mm (4 inch). For S-L, samples are all tested at t/2.
  • B 50.8 mm (2 inch).
  • the cross section is divided into elementary rectangles of dimensions A and B; A always being the largest dimension of the elementary rectangle and B being regarded as the thickness of the elementary rectangle.
  • structural member is a term well known in the art and refers to a component used in mechanical construction for which the static and/or dynamic mechanical characteristics are of particular importance with respect to structure performance, and for which a structure calculation is usually prescribed or undertaken. These are typically components the rupture of which may seriously endanger the safety of the mechanical construction, its users or third parties.
  • structural members comprise members of the fuselage (such as fuselage skin), stringers, bulkheads, circumferential frames, wing components (such as wing skin, stringers or stiffeners, ribs, spars), empennage (such as horizontal and vertical stabilizers), floor beams, seat tracks, and doors.
  • the process of the invention comprises different steps.
  • a first step aims at preparing a bath of molten alloy metal comprising, or advantageously consisting essentially of in weight % (wt. %) Zn 6.65 - 7.45, Mg 1.35 - 1.75, Cu 1.85 - 2.35, Zr 0.04 - 0.14, Mn 0 - 0.5, Ti 0 - 0.15, V 0 - 0.15, Cr 0 - 0.25, Fe ⁇ 0.05, Si ⁇ 0.05% with a Fe+Si ⁇ 0.08 % and other impurities ⁇ 0.05 each and ⁇ 0.15 total, remainder aluminum.
  • said bath of molten alloy metal comprises, or advantageously consists essentially of in weight % (wt. %) Zn 6.90 - 7.30, Mg 1.35 - 1.75, Cu 1.95 - 2.35, Zr 0.04 - 0.14, Mn 0 - 0.5, Ti 0 - 0.15, V 0 - 0.15, Cr 0 - 0.25, Fe ⁇ 0.05, Si ⁇ 0.05% with a Fe+Si ⁇ 0.08 % and other impurities ⁇ 0.05 each and ⁇ 0.15 total, remainder aluminum.
  • said bath of molten alloy metal comprises, or advantageously consists essentially of in weight % (wt. %) Zn 6.90 - 7.25, Mg 1.35 - 1.75, Cu 2.00 - 2.35, Zr 0.04 - 0.14, Mn 0 - 0.5, Ti 0 - 0.15, V 0 - 0.15, Cr 0 - 0.25, Fe ⁇ 0.05, Si ⁇ 0.05% with a Fe+Si ⁇ 0.08 % and other impurities ⁇ 0.05 each and ⁇ 0.15 total, remainder aluminum.
  • Said molten alloy metal is then cast to obtain a slab or a billet.
  • a slab according to the invention is parallelepipedal; it can be also called “ingot”.
  • Said slab or billet is then homogenized.
  • the homogenization is preferably performed with at least one step at a temperature from about 450°C to about 510 °C typically for 5 to 30 hours or preferentially from about 470°C to about 500 °C for 8 to 20 hours or even more preferably between 470°C to 490°C for 8 to 20 hours.
  • Said homogenized slab or billet is hot worked to obtain a wrought product with a final thickness of at least 25 mm, preferably from about 25 mm to about 200 mm, more preferably from about 70 mm to about 160 mm, even more preferably from about 70 mm to about 102 mm.
  • Said wrought product is a rolled product or an extruded product or a forged product.
  • the forged product can be obtained directly by forging the billet or ingot or from the rolled product (e.g. first rolled and then forged), or from the extruded product (e.g. first extruded then forged).
  • the homogenized slab is hot rolled to obtain a rolled product with a final thickness of at least 25 mm, preferably from about 25 mm to about 200 mm, more preferably from about 70 mm to about 160 mm, even more preferably from about 75 mm to about 102 mm or between about 70 mm to about 80 mm.
  • Hot rolling is preferably done in one or multiple stages with an entry temperature preferably comprised from about 380°C to about 460 °C and preferentially from about 400°C to about 450 °C.
  • Said wrought product e.g. rolled product or an extruded product and/or a forged product
  • a solution heat treated wrought product preferably at a temperature from 460°C to about 510 °C or preferentially from about 470°C to about 500 °C or even more preferably between 470°C to 490°C typically for 1 to 10 hours depending on thickness.
  • Said solution heat treated wrought product is then quenched to obtain a quenched wrought product, preferably in water at room temperature.
  • Said quenched wrought product is then stress relieved to obtain a stress relieved wrought product.
  • Stress relief is obtained by controlled stretching or compression with a permanent plastic deformation of preferably less than 5% and preferentially from 1 to 4%, more preferentially between 2 to 3 %.
  • Said stress relieved wrought product is then artificially aged with a total equivalent aging time t(eq) at 155°C from 24 hours to 45 hours, preferably from 24 hours to 34 hours, even more preferably from 26 hours to 30 hours
  • the total equivalent time t(eq) at 155°C being defined by the formula: Jexp(-16000 / T) dt ) exp(- 16000 / Tref) where T is the instantaneous temperature in °K during aging and T re f is a reference temperature selected at 155 °C (428 °K), t(eq) is expressed in hours.
  • the total equivalent time t(eq) at 155°C is defined by the formula:
  • This formula involves an integral with respect to time t of the function exp(-16000/T), where T is the instantaneous temperature in Kelvin.
  • the integral can be calculated using numerical integration. Methods of numerical integration are for instance described in "Numerical Recipes - The Art of Scientific Computing - Third Edition” by Press W. H. et al published by Cambridge University Press in 2007. This book describes different numerical methods for integrating a function (paragraph 4).
  • One simple method that can be used to calculate the equivalent time is the trapezoidal rule (see paragraph 4.1.1, equation 4.1.3).
  • the integral can be calculated analytically, like for instance when aging is considered as a step at a constant temperature.
  • t(eq) tl * exp (- 16000/T1 + 16000/428) + t2 * exp(-16000/T2+16000/428)
  • the total equivalent aging time t(eq) at 155°C is at least 24 hours, preferably at least 25 hours, or 26 hours or even more preferably at least 27 hours.
  • the total equivalent aging time t(eq) at 155°C is less than 45 hours, preferably less than 40 hours, 39 hours, 38 hours, 37 hours, 36 hours, 35 hours, 34 hours, 33 hours, 32 hours, 31 hours, or even more preferably less than 30 hours. Any combination of minimum and maximum above listed can permit to obtain the best compromise of toughness and yield strength at ambient temperature and cryogenic temperatures.
  • Aging treatment is advantageously carried out in two steps, with a first step at a temperature comprised from 100 to 150°C, preferably from 110 to 130 °C, for 3 to 20 hours, preferably for 3 to 10 hours and a second step at a temperature comprised from 140 to 180 °C, preferably from 140 to 170 °C for 6 to 90 hours, preferably from 150 to 165 °C for 9 to 50 hours.
  • the product of the invention with his specific composition in particular with a Fe and Si content ⁇ 0.08 wt. %, when combined with an appropriately designed artificial aging treatment, makes it possible to obtain a product with a better compromise between tensile yield strength and toughness at ambient temperature and cryogenic temperatures, in particular a better compromise between tensile yield strength in the rolling direction (L direction) and toughness in L-T direction at ambient temperature.
  • the present alloy according to the invention contains from 6.65 to 7.45 wt. % Zn.
  • the present alloy according to the invention contains from 1.35 to 1.75 wt. % Mg.
  • a minimum Mg content of 1.35 wt. % and preferably 1.40 wt. % or 1.50 wt. % or even 1.60 wt. % is needed to obtain sufficient strength.
  • the Mg content should not exceed 1.75 wt. % and preferably 1.70 wt. % to obtain the sought balance of properties in particular toughness and elongation.
  • the present alloy according to the invention contains from 1.85 to 2.35 wt. % Cu.
  • a minimum Cu content of 1.85 wt. %, preferably 1.95, more preferably 2.0 wt. % or even more preferably 2.1 wt. % is needed to obtain sufficient strength.
  • the Cu should not exceed 2.35 wt. % and preferably 2.30 % or even more preferably 2.25 wt. % to avoid quench sensitivity.
  • the alloy of the present invention further contains from 0.04 to 0.14 wt.% Zr, which is typically used for grain size control.
  • the Zr content should preferably comprise at least about 0.07 wt. %, and preferentially about 0.09 wt.% in order to limit the recrystallization, but should advantageously remain below about 0.12 wt.% in order to reduce problems during casting.
  • Titanium can usually be added up to 0.15 wt.% if desired during casting in order to limit the as- cast grain size.
  • Ti can be associated with either boron or carbon
  • the present invention may typically accommodate up to about 0.06 wt. % or about 0.05 wt.%Ti.
  • the Ti content is from about 0.02 wt.% to about 0.06 wt.% and preferentially from about 0.03 wt.% to about 0.05 wt.%.
  • Manganese up to 0.5 wt.% may be added but it is preferentially avoided and is generally kept below about 0.05 wt.%, preferentially below about 0.04 wt.%. and more preferentially below about 0.03 wt.%.
  • Vanadium up to 0.15 wt.% may be added but it is preferentially avoided and is generally kept below about 0.05 wt.%, preferentially below about 0.04 wt.%. and more preferentially below about 0.03 wt.%.
  • Chromium up to 0.25 wt.% may be added but it is preferentially avoided and is generally kept below about 0.05 wt.%, preferentially below about 0.04 wt.%. and more preferentially below about 0.03 wt.%.
  • the present alloy may contain iron and silicon which affect fracture toughness properties. It was observed that iron and silicon content (e.g. Fe + Si content) must not exceed about 0.08 wt. %, preferably about 0.07 wt. %, more preferably 0.06 wt. % and even more preferably 0.05 wt. % to achieve a better compromise between tensile yield strength and toughness, small drop (less than 10%) in fracture toughness at cryogenic temperature, and very little increase in fatigue crack growth rate under high humidity conditions when compared to fatigue under ambient lab conditions. The inventors found that for the selected composition and Fe+ Si content below 0.08 wt.
  • iron and silicon content e.g. Fe + Si content
  • iron and silicon content is from 0.03% to 0.08 wt. %, preferably from 0.03% to 0.07 wt. %, more preferably from 0.03% to 0.06 wt. % and even more preferably from 0.03% to 0.05 wt. %.
  • the present alloy may contain an iron and silicon content (e.g. Fe + Si content) from 0.04% to 0.08 wt. %, preferably from 0.04% to 0.07 wt. %, more preferably from 0.04% to 0.06 wt. % and even more preferably 0.04% to 0.05 wt. %.
  • the present alloy may contain an iron and silicon content (e.g. Fe + Si content) from 0.05% to 0.08 wt. %, preferably from 0.05% to 0.07 wt. %, more preferably from 0.05% to 0.06 wt. %.
  • an iron and silicon content e.g. Fe + Si content
  • the present alloy may include up to 0.05 wt. % Si, preferentially up to 0.03 wt. %.
  • the present alloy may include up to 0.05 wt. % Fe, preferentially up to 0.03 wt. %.
  • the present alloy may include incidental impurities.
  • incidental impurities can include relatively small amounts, less than 0.05 wt. %, or less than 0.01 wt. % of other elements with a total of less than 0.15 wt% total of the total weight of the 7xxx aluminum alloy product. Incidental impurities can be present without departing from the scope of the invention.
  • the present invention finds particular interest for rolled product, in particular with a thickness of at least 25 mm, preferentially from 25 mm to 200 mm, more preferably from 70 mm to 200 mm, or from 70 mm to 160 mm, even more preferably from 70 mm to 102 mm.
  • the rolled product with a thickness of at least 25 mm, preferentially from 25 mm to 200 mm more preferably from 70 mm to 200 mm, or from 70 to 160 mm, even more preferably from 70 mm to 102 mm according to the invention has advantageously the following properties:
  • the rolled product has advantageously a yield strength of at least 450 MPa in the rolling direction L.
  • a yield strength in the transverse direction LT of at least 410 MPa, even more preferably of at least 420 MPa.
  • the rolled product according to the invention displays a surprising small drop in both fracture toughness and elongation from room temperature down to liquid nitrogen temperature.
  • the rolled product according to the invention displays a toughness Klc(T- L) in MPa.Vm, at cryogenic temperature of about -196 °C, measured according to ASTM standard E399 2020 which is reduced by less than 10 %, preferably by less than 8%, more preferably by less than 7 % in comparison with Klc(T-L) in MPa.Vm, measured at room temperature according to ASTM standard E399 -2020.
  • the rolled product according to the invention displays a toughness Klc(T-L) in MPa.Vm, at cryogenic temperature of about -196 °C, measured according to ASTM standard E399 -2020 higher than -0.15*t +45 MPa.Vm , preferably higher than - 0.15*t+49 MPa.Vm, even more preferably higher than -0.15*t+55 MPa, where t is the thickness of the rolled product in mm.
  • the rolled product according to the present invention or the product obtained by the process according to the invention is advantageously used as or incorporated in structural members for the construction of aircraft or spacecraft.
  • the products according to the invention are used in wing ribs, spars and frames.
  • the rolled products according to the present invention are welded with other rolled products to form wing ribs, spars and frames.
  • the rolled product according to the invention or the product obtained by the process according to the invention is advantageously used in structural member used at cryogenic temperature, typically cryogenic tank.
  • cryogenic temperature typically cryogenic tank.
  • the rolled product according to the invention or the product obtained by the process according to the invention is advantageous to manufacture mechanical parts, such as pistons or impellers, that are used for gas compression at cryogenic temperature, in particular for hydrogen or oxygen or nitrogen or methane or natural gas compression.
  • the rolled product according to the invention or the product obtained by the process according to the invention is used for the manufacture of stationary inland storage tanks or of transportation storage tanks of liquid gas such as liquid hydrogen or liquid oxygen or liquid nitrogen or liquid methane or liquid natural gas.
  • Transportation storage tanks are movable tanks for example tanks used in cars or trucks or lorries or trains or ships or aircrafts or rockets when the liquid gas is used as a fuel or tanks used in trucks or lorries or trains or ships to move liquid gas.
  • Example 1 Two ingots were cast with two compositions A and B according to the invention. The ingots were homogenized and hot rolled to 76.2 mm (Al) and 152.4 mm (B3) in thickness, followed by a solution heat treatment, stretching and final aging according to the process of the invention. The chemistry and process information for these two lots are shown respectively in Table 1 and Table 2.
  • Figure 1 shows the evolution of toughness Ki c (T-L) at cryogenic temperature versus the thickness of the plate. It can be observed that Al and Bl specimen display a toughness Klc(T-L) in MPa.Vm, at cryogenic temperature of about -196 °C higher than -15*t +45 MPa.Vm , preferably higher than - 0.15*t+49 MPa.Vm, even more preferably higher than -0.15*t+55 MPa, where t is the thickness of the product in mm.
  • Figure 2 shows the compromise at Room temperature (RT) between tensile yield strength in the rolling direction (L) and toughness in L-T direction, measured respectively at quarter thickness and mid thickness for Al and Cl plate.
  • RT Room temperature
  • L tensile yield strength in the rolling direction
  • L-T direction toughness in L-T direction
  • Figure 3 shows the compromise between tensile yield strength in the transverse direction (LT) and the toughness in T-L, measured at room temperature and at liquid nitrogen temperature of -196°C. It can be observed that Al plates exhibits a lower drop in toughness than DI plate. It is attributed to the chemical composition, in particular the lower Fe + Si content.
  • compositions A, C, G, H, J, K, M were cast and transformed; respective details of composition and process are listed in Tables 14 and 15. All these cast were transformed into plates with thicknesses from 70 to 102 mm.
  • Alloys C, G, H correspond to prior art alloys and J, K and M are compositions according to the invention.
  • Alloy A is similar from example 1.
  • samples having a composition according to the invention and processed according to the invention are represented with a black diamond (Al-a, Jl-A, K2-a).
  • Samples having a composition according to the invention but processed differently are represented by an empty diamond (M2-b).
  • a triangle symbol is used to represent compositions which differ from the invention by Fe+Si content above 0.08 wt. % (Cl-a and Cl-b).
  • a round circle symbol is used to represent compositions which differ from the invention by main alloying elements (G2- a, H2-a).
  • Triangle or round circle symbols are empty if the process differs from the invention, i.e. equivalent time at 155°C below 23 h or with full symbol if the process is according to the invention.
  • Figure 4 represents the effect of Fe+Si content on Ki c (L-T) for products artificially aged with a total equivalent time at 155°C higher than 24h.
  • thickness range between about 70 mm to about 102 mm, it is observed that for all cases, decreasing the amount of Fe+Si permits to improve the toughness Ki c (L-T).
  • the trend is significantly more marked on samples Al-a, Jl-a, K2-a processed according to the invention, artificially aged with a total equivalent time at 155°C from 24h to 45 hours and with a composition, in particular a Fe+Si content less or equal to 0.08 wt.%.
  • slope Al is representative of the effect of (Fe+Si) on Ki c L-T.
  • Sample Cl-a aged with an equivalent time of 24.4h at 155°C exhibits a lower toughness Ki c (L-T). The inventors attribute this behavior to its Fe+Si content.
  • slope A2 is representative of the effect of major alloying elements on Ki c L-T.
  • the slope A2 is lower than slope Al.
  • the inventors attribute this behavior to the synergetic effect of composition selection, in particular Zn and Mg content, and Fe+Si content.
  • Figure 5 represents the effect of Fe+Si content on Ki c (L-T).
  • Arrows (ATI) from M2-b to K2-a) and (AT2) from Cl-b to Cl-a represent respectively the effect of total equivalent time at 155°C at iso Fe+Si content for a composition according to the invention or the prior art. It is well observed that increasing total equivalent time at 155°C of aging permits to increase the toughness. However, this trend is more pronounced for the composition with a Fe+Si content below 0.08 wt. % according to the invention (arrow ATI).
  • Samples Al-a, Jl-a and K2-a whose thicknesses are between 75 mm and 102 mm present a toughness Kic (L-T) higher than -0.25t+65 MPa. ⁇ /m, preferably higher than -0.25t +68 MPa. ⁇ /m, and even more preferably higher than -0.25t+72 MPa. ⁇ /m, where t is the thickness plate in mm (figure 6).
  • Samples M2-b, K2-a, H2-a exhibit a lower toughness Klc (L-T) than samples according to the invention despite a Fe+Si content lower than 0.08%.
  • the inventors attribute this behavior to the composition and/or the artificial aging conditions which do not fulfill a total equivalent time at 155°C between 24h and 45h.
  • Fatigue crack growth rate of B3 plate mentioned in example 1 was evaluated and compared with a reference product 03 of similar thickness 152.4 mm (6 inch). Alloys O and B are according to the invention (Table 15) with a Fe+Si content below 0.08 wt. %. 03 plate is processed similarly to B3 plate, except the artificially aging conditions which gives an equivalent aging time at 155°C of 19.9h (Table 16).
  • Fatigue crack growth rate was evaluated based on ASTM E647.
  • the coupons orientation is L-T.
  • the standard Compact Tension, i.e. C(T), coupon dimension was used for test.
  • the dimension B is 7.6 mm (0.3 inch) and W is 50.8 mm (2 inch) for all test coupons.
  • RH relative humidity
  • Figure 7 and Figure 8 disclose respectively the fatigue crack growth rate evolution of plate 03 and B3 versus environment conditions. It is observed that a product with a composition chosen according to the invention aged with an equivalent time at 155°C higher than 24h (B3, Figure 8) exhibits a similar fatigue crack growth rate whatever relative humidity considered. The product aged for an equivalent time at 155°C below 23h (03, Figure 7) shows a significant dependence on humidity.

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Abstract

La présente invention concerne un produit d'alliage d'aluminium 7xxx corroyé comprenant en % en poids du Zn à hauteur de 6,7 à 7,4, du Mg à hauteur de 1,35 à 1,75, du Cu à hauteur de 1,85 à 2,35, du Zr à hauteur de 0,04 à 0,14, du Mn à hauteur de 0 à 0,5, du Ti à hauteur de 0 à 0,15, du V à hauteur de 0 à 0,15, du Cr à hauteur de 0 à 0,25, du Fe à une proportion ≤ 0,05, du Si à une proportion ≤ 0,05 avec Fe + Si ≤ 0,08 % et artificiellement vieilli, le temps de vieillissement équivalent total t(eq) à 155 °C étant compris entre 24 heures et 45 heures qui permet d'optimiser le compromis entre la limite d'élasticité à la traction et la ténacité avec une ténacité à la rupture cryogénique et une résistance à la fatigue améliorées dans un environnement corrosif.
PCT/EP2023/085062 2022-12-12 2023-12-11 Produits corroyés 7xxx présentant un compromis amélioré des propriétés de traction et de ténacité et procédé de production WO2024126341A1 (fr)

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US202263387018P 2022-12-12 2022-12-12
US63/387,018 2022-12-12
EP22213912.3A EP4386097A1 (fr) 2022-12-12 2022-12-15 Produits ecrouis en alliage 7xxx avec un compromis amélioré de propriétés de traction et de ténacité et procédé de production
EP22213912.3 2022-12-15
US202363509297P 2023-06-21 2023-06-21
US63/509,297 2023-06-21

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