EP3495520B1 - Kostengünstige, im wesentlichen zr-freie aluminium-lithium-legierung für dünnblech mit hoher formbarkeit - Google Patents

Kostengünstige, im wesentlichen zr-freie aluminium-lithium-legierung für dünnblech mit hoher formbarkeit Download PDF

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EP3495520B1
EP3495520B1 EP18210045.3A EP18210045A EP3495520B1 EP 3495520 B1 EP3495520 B1 EP 3495520B1 EP 18210045 A EP18210045 A EP 18210045A EP 3495520 B1 EP3495520 B1 EP 3495520B1
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aluminum
alloy
lithium alloy
thickness
gage
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French (fr)
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EP3495520C0 (de
EP3495520A1 (de
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Zhengdong Long
Philippe Lassince
Robert A. Matuska
Florence Andrea BALDWIN
Ravi Rastogi
Roy Austin Nash
Jason Nicholas SCHEURING
Gary D. HOLMESMITH
Yansheng Liu
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Kaiser Aluminum Fabricated Products LLC
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Kaiser Aluminum Fabricated Products LLC
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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
    • C22F1/057—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 copper as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D25/00—Working sheet metal of limited length by stretching, e.g. for straightening
    • 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
    • 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
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • 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
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/001—Aluminium or its alloys

Definitions

  • This present invention generally relates to Aluminum-Copper-Lithium-Magnesium based alloy products.
  • Al-Li aluminum-lithium
  • microstructure and texture are strongly affected by chemical composition of the alloy and most of the manufacturing steps, i.e. homogenization, hot and cold rolling, annealing, solution heat treatment, and stretching.
  • Al-Li sheet is much more difficult to manufacture than conventional 2xxx and 7xxx alloys. This is the result of thin Al-Li sheets being more sensitive to rolling cracking, surface oxidation, and distortion. Due to these limitations, there is a small processing window that can be used to optimize the desired microstructure and texture.
  • US 2016/115576 A1 discloses Al-Cu-Li-Mg alloys capable of producing low cost and high strength thin sheet products.
  • the desired metallurgical structure would have fine recrystallized grains. This is a critical feature in obtaining the desired formability.
  • the grain structure can be affected by both chemistry and processing parameters. From a chemistry perspective, it is well known that Zr is widely added as a grain structure control element in most Al-Li and 7xxx alloy series. In " International Alloy Designation and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys" published up to January 2017 , there are 29 active Al-Li alloys registered in the Aluminum Association. All 29 alloys contain Zr. Meanwhile, there are numerous Zr containing Al-Li patent and patent applications.
  • Al-Li alloy products are also challenging.
  • Silver (Ag) is added to many new generation Al-Li alloys in order to improve the final product properties, adding significant alloy costs.
  • two of them (AA2198 and AA2195) contain Ag.
  • Ag is very popular for Al-Li alloys as demonstrated by a significant amount of Al-Li alloy patents and patent applications.
  • An aluminum-lithium alloy for aircraft fuselage sheet or light-gauge plate applications are known based on the registered AA2198 Al-Li sheet alloy. This alloy comprises 0.1 to 0.8 wt. %Ag, so it is not considered a low cost alloy. Furthermore it has a relatively low strength for an Al-Li alloy.
  • An aluminum-copper-magnesium alloy having ancillary additions of lithium is known based on the registered AA2060 Al-Li alloy.
  • the claimed level for lithium is only from 0.01 to 0.8 wt. %; because of this limited addition of lithium, this is not considered to be really a "lowdensity" alloy.
  • An improved aluminum-copper-lithium alloys is known based on the registered AA2055 Al-Li alloy. This alloy comprises 0.3 to 0.7 wt. %Ag, so it is not considered to be a low cost alloy. The alloy is used for high-strength extrusions.
  • AA2050 Al-Li plate alloy. This is not considered to be a low-cost alloy.
  • AA2050 is designed for Al-Li plate products from 12.7mm (0.5") to 127mm (5') and includes 0.15 to 0.35 wt. % Ag.
  • the alloy is suitable for plate in thickness range of 30mm (1.2") to 100mm (3.9").
  • Another aluminum alloy is known including 0.05 to 1.2 wt. % Ag, so it is not considered to be a low-cost alloy.
  • the main advantage of this alloy is to have high strength, ductility, excellent weldability, and natural aging response.
  • the present invention provides a low cost, high formability, substantially Zr-free, low density Al-Li alloy suitable for making transportation components, such as aerospace structural components.
  • Aluminum-lithium alloys of the invention comprise from 3.2 to 4.1 wt. % Cu, 1.0 to 1.8 wt. % Li, 0.8 to 1.2 wt. % Mg, 0.10 to 0.50 wt. % Zn, 0.10 to 1.0 wt. % Mn, up to 0.12 wt. % Si, up to 0.15 wt. % Fe, up to 0.15 wt. % Ti, up to 0.15 wt. % incidental elements, with the total of these incidental elements not exceeding 0.35 wt. %, and the balance being aluminum.
  • Ag should not be more than 0.1 wt. % and is preferably not intentionally added.
  • Zr should not be more than 0.05 wt. % and is preferably not intentionally added.
  • Mg is at least equal to or higher than 2*Zn in weight percent in the invented alloy. Methods for manufacturing wrought aluminum-lithium alloys products of the present invention are also provided.
  • the aluminum-lithium alloy of the present invention having no Ag, or very low amounts of not intentionally added Ag, no Zr, or very low amounts of not intentionally added Zr, and high Mg content is capable of producing 0.01 to 0.249 inch thickness sheet products with excellent formability, low density, low cost, high strength, and good damage tolerance properties and corrosion resistance.
  • Another aspect of the present invention is a method to manufacture aluminum-lithium alloys of the present invention.
  • the present invention is directed to aluminum-lithium alloys, specifically aluminum - copper - lithium - magnesium alloys.
  • the aluminum-lithium alloy of the present invention comprises from 3.2 to 4.1 wt. % Cu, 1.0 to 1.8 wt. % Li, 0.8 to 1.2 wt. % Mg, 0.10 to 0.50 wt. % Zn, 0.10 to 1.0 wt. % Mn, up to 0.12 wt. % Si, up to 0.15 wt. % Fe, up to 0.15 wt. % Ti, up to 0.15 wt. % incidental elements, with the total of these incidental elements not exceeding 0.35 wt. %, and the balance being aluminum.
  • the aluminum-lithium alloy of the present invention shall be "substantially Zr-free", meaning that Zr should not be intentionally added and should not be more than 0.05 wt. % as an incidental element.
  • Mg is at least equal or higher than 2*Zn in weight percent in the invented alloy.
  • the aluminum-lithium alloy comprises from 3.4 to 3.9 wt.% Cu, 1.1 to 1.7 wt.% Li, 0.8 to 1.2 wt.% Mg, 0.20 to 0.50 wt. % Zn, 0.20 to 0.6 wt. % Mn, a maximum of 0.12 wt.% Si, a maximum of 0.15 wt.% Fe.
  • Such embodiment of the aluminum-lithium alloy would also have Mg content that is at least equal to or higher than 2*Zn in weight percent.
  • the aluminum-lithium alloy may include less than 0.1 wt. % of not intentionally added Ag, preferably less than 0.05 wt. % of not intentionally Ag, and more preferably less than 0.01 wt.
  • the aluminum-lithium alloy may include less than 0.05, or 0.04, or 0.03, or 0.02, or even 0.01 wt. % of not intentionally Zr. In a preferred embodiment, no Ag and Zr are intentionally added to the aluminum-lithium alloy.
  • the aluminum-lithium alloy of the present invention can be used to produce wrought products, preferably, having a thickness range of 0.01-0.249 inch, more preferably in the thickness range of 0.01-0.125 inch.
  • the aluminum-lithium alloys of the present invention are wrought products having excellent formability, high strength, and good damage tolerance and corrosion properties.
  • the aluminum-lithium alloy of the present invention can be used for the fabrication of sheet metal components using several manufacturing processes. Common methods are roll forming, stretch forming, hammer drop forming, stamping, draw forming, and hydroforming.
  • Example components that can be made from these forming methods include but are not limited to, fuselage frames, fuselage stringers, contoured fuselage skins, constant cross-section skins, electrical wire harnesses clips, brackets for cable used in control systems, attachment points for interior components to primary structures such as fuselage frames, shear ties for attaching fuselage frames to fuselage skins, shear ties for attaching wing ribs to wing skins, wing ribs, clips to attach wing ribs to wing spars, empennage skins, empennage ribs, nacelle skins, engine leading edge inlet skins, pressure bulkhead skins, pylon skins, bracketry for attaching avionics to structural components, bracketry for attaching passenger oxygen systems, avionics enclosures, shelving for avionics components, etc.
  • the present application discloses an alloy that is substantially Zr-free without the intentional addition of Zr, which is almost exclusively added in all the 29 active Al-Li alloys that have been registered in Aluminum Association based on " International Alloy Designation and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys” published up to January 2017 .
  • Zr is widely believed to form Al 3 Zr dispersoid particles to control the grain structure and also potentially improve strength
  • the exact impact of Zr in complicated Al-Li alloys thin products is not clear or fully understood.
  • the presently disclosed substantially Zr-free Al-Li alloy innovatively changes the metallurgical approach to obtain a desired grain structure for excellent formability and strength suitable for aerospace applications.
  • Zr is not intentionally added in the aluminum-lithium alloy of the present invention.
  • Zr may exist in the alloy as a result of a non-intentionally added incidental element.
  • the Zr should not be more than 0.05 wt. %.
  • the aluminum-lithium alloy may include alternate embodiments having less than 0.05 wt.% Ag, less than 0.04 wt.% Zr, less than 0.03 wt.% Zr, less than 0.02 wt.% Zr or less than 0.01 wt.% Zr.
  • Copper is added to the aluminum-lithium alloy in the present invention in the range of 3.2 to 4.1 wt. %, mainly to enhance the strength but also to improve the combination of strength, formability and fracture toughness.
  • An excessive amount of Cu can result in unfavorable intermetallic particles which can negatively affect material properties such as ductility, formability, and fracture toughness. In these cases the interaction of Cu with other elements such as Li and Mg also must also be considered.
  • the present invention includes alternate embodiments wherein the upper or lower limit for the amount of Cu may be selected from 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, and 4.1 wt.%.
  • the Cu is from 3.4 to 3.9 wt. % to provide compositions that enhance specific product performance while maintaining relatively high performance in the remaining attributes as compared to the prior art.
  • Lithium is added to the aluminum-lithium alloy in the present invention in the range of 1.0 to 1.8 wt.%.
  • the primary benefit for adding Li element is to reduce the density and increase the elastic modulus and strength.
  • Li is critical in improving the strength, damage tolerance and corrosion performance. Too high an amount of Li content, however, can negatively impact fracture toughness, anisotropy of tensile properties, and formability.
  • the present invention includes alternate embodiments wherein the upper or lower limit for the amount of Li may be selected from 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 wt. %. In one preferred embodiment, Li is in the range of 1.1 to 1.7 wt. %.
  • Mg is added to the aluminum-lithium alloy in the present invention in the range of 0.8 to 1.2 wt. %.
  • the primary purpose of adding Mg is to enhance the strength with the secondary purpose of slightly reducing the density.
  • too high an amount of Mg can reduce Li solubility in the matrix, thus negatively impacting the aging potential for higher strength.
  • the present invention includes alternate embodiments wherein the upper or lower limit for the amount of Mg may be selected from 0.8, 0.9, 1.0, 1.1, and 1.2 wt. %.
  • the addition of low levels of Zn in the aluminum-lithium alloy of the present invention aims at improving corrosion resistance. It is believed that Zinc goes into solid solution within the grains and shifts the pitting potential of the matrix to less noble and decreases the electrochemical potential difference between the grain boundary and the matrix, thus improving static and dynamic corrosion Properties.
  • the addition of Zn is from 0.1 to 0.5 wt%.
  • the present invention includes alternate embodiments wherein the upper or lower limit for the amount of Zn may be selected from 0.1, 0.2, 0.3, 0.4, and 0.5 wt. %. In one preferred embodiment, Zn is in the range of 0.2 to 0.5 wt. %.
  • Ag is not intentionally added in the aluminum-lithium alloy of the present invention.
  • Ag may exist in the alloy as a result of a non-intentionally addition. In this case, the Ag should not be more than 0.10 wt. %.
  • the present invention includes alternate embodiments wherein the aluminum-lithium alloy may include less than 0.1 wt. % of not intentionally added Ag, less than 0.05 wt. % of not intentionally added Ag, or less than 0.01 wt. % of not intentionally added Ag.
  • the prior art teaches that Ag is necessary to improve the final product properties and is therefore included in many aluminum-lithium alloys as well as many patents and patent applications.
  • Ag significantly increases the cost of the alloys.
  • Ag is not intentionally included in order to reduce the cost. It is surprising to find that the aluminum-lithium alloy of the present invention, without the addition of Ag for providing low cost, can be used to produce high strength, high formability, excellent corrosion resistance, and good damage tolerance performance sheet products suitable for structural applications particularly in aerospace.
  • Mn is intentionally added to improve the grain structure for better mechanical isotropy and formability.
  • the present invention includes alternate embodiments wherein the upper or lower limits for the amounts of Mn may be selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0 wt. %.
  • the addition of Mn is in the range from 0.20 to 0.6 wt. %.
  • Ti can be added up to 0.15 wt. %.
  • the purpose of adding Ti is mainly for grain refinement in casting.
  • the present invention includes alternate embodiments wherein the upper limit for the amount of Ti may be selected from 0.01, 0.02, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 and 0.15 wt. % Ti.
  • Si and Fe may be present in the aluminum-lithium alloy of the present invention as impurities but are not intentionally added. When present their content must be ⁇ 0.12 wt.% for Si, and ⁇ 0.15 wt. % for Fe, preferably ⁇ 0.05 wt.% for Si and ⁇ 0.08 wt.% for Fe.
  • the aluminum-lithium alloy of the present invention includes a maximum content of 0.12 wt.% for Si, and 0.15 wt.% for Fe. In one preferred embodiment, a maximum contents are 0.05 wt.% for Si and 0.08 wt.% for Fe.
  • the aluminum-lithium alloy of the present invention may also include low levels of "incidental elements” that are not included intentionally.
  • the "incidental elements” means any other elements except those described above (Al, Cu, Li, Mg, Zr, Zn, Mn, Ag, Fe, Si, and Ti).
  • the low cost, high formability, substantially Zr-free Al-Li alloy of the present invention may be used to produce wrought products.
  • the rolled products may be manufactured using known processes such as casting, homogenization, hot rolling, optionally cold rolling, solution heat treating and quenching, optionally stretching and levelling, and ageing treatments.
  • the ingot may be cast by traditional direct chill (DC) casting method.
  • the ingot may be homogenized at temperatures from 454 to 549°C (850 to 1020°F), preferably from 482 to 543°C (900 to 1010°F), and more preferably from 496 to 538°C (925 to 1000°F).
  • the hot rolling temperature may be from 343 to 499°C (650 to 930°F), preferably from 357 to 482°C (675 to 900°F), and more preferably from 371 to 466°C (700 to 870°F).
  • the optional cold rolling may be needed particularly for the thinnest gauges.
  • the cold work reduction can be from 20% to 95%, preferably from 40% to 90%.
  • the products may be solution heat treated at temperature range of 454 to 543°C (850 to 1010°F), preferably 482 to 538°C (900 to 1000°F), and more preferably 493 to 532°C (920 to 990°F).
  • the wrought products are cold water quenched to room temperature and may be optionally stretched or cold worked up to 15%, preferably from 2 to 8%.
  • the quenched product may be subjected to any aging practices known by those skilled in the art including, but not limited to, one-step aging practices that produce a final desirable temper, such as T8 temper, for better combination of strength, fracture toughness, and corrosion resistance which are highly desirable for aerospace members.
  • the aging temperature can be in the range of 121 to 205°C (250 to 400°F) preferably from 135 to 193°C (275 to 380°F), and more preferably from 149 to 182°C (300 to 360°F) and the aging time can be in the range of 2 to 60 hours, preferably from 10 to 48 hours.
  • the unique chemistry along with proper processing of the aluminum-lithium alloy of the present patent application result in thin sheet with surprising material characteristics such as ideal crystallographic texture, which strongly affect material performance such as formability.
  • the texture is normally evaluated by X-Ray diffractometer facility and the volume fractions of texture components can be determined.
  • the most common texture components for aluminum alloy sheet include Cube: ⁇ 001 ⁇ , ⁇ 100>; R-Cube: ⁇ 001 ⁇ , ⁇ 110>; Goss: ⁇ 011 ⁇ 100>; Brass: ⁇ 011 ⁇ 211>; S: ⁇ 123 ⁇ 634>, Copper- ⁇ 112 ⁇ 111>.
  • Brass and S textures are “hard” textures since they are “hard” to be deformed and Cube and R-Cube are “soft” textures since they are “easier” to be deformed.
  • the ratio of "soft” / "hard” texture components is critical for formability: the higher this ratio, the better the formability.
  • the ratio of "soft" / "hard” texture of T3 temper components is higher than "0.75 - 0.5 * gage” and "0.85 - 5.0 * gage” at sheet quarter thickness (th/4) and center thickness (th/2) respectively.
  • this ratio is higher than "0.83 - 0.5 * gage” and "0.98 - 5.0 * gage” at quarter thickness (th/4) and center thickness (th/2) respectively. In a more preferred embodiment, this ratio is higher than "0.9 - 0.5 * gage” and "1.1 - 5.0 * gage” at quarter thickness (th/4) and center thickness (th/2) respectively.
  • the unit of the gage is inch.
  • the minimum LT bend ratio is less than "24.30-0.0292 * "Specific LT TYS”", and the minimum L bend ratio is less than "13.11 - 0.0146 * “Specific L TYS””. In a preferred embodiment, the minimum LT bend ratio is less than "23.65 - 0.0292 * "Specific LT TYS”", and the minimum L bend ratio is less than "12.88 - 0.0146 * "Specific L TYS””.
  • the Specific LT TYS equals the Long-Transverse Tensile Yield Strength (in ksi) divided by density (in lb/in 3 ).
  • the Specific L TYS equals the Longitudinal Tensile Yield Strength (in ksi) divided by density (in lb/in 3 ). So the unit of specific strength is "ksi/(lb/in 3 )”.
  • T3 temper sheet is primarily focused for the aluminum-lithium alloy of the present invention.
  • the O temper is commonly provided from aluminum producers (aluminum mill) to airframe manufacturers.
  • the O temper sheet is processed in different ways such as forming, solutionizing, cold water quenching, and aging.
  • the T3 temper sheet provided has a significant cost advantage since it eliminates the process of solutionizing and cold water quenching process steps at the airframer.
  • the ingots were homogenized at temperatures from 496 to 538°C (925 to 1000°F).
  • the hot rolling temperatures were in the range of 399 to 466°C (750 to 870°F).
  • the ingots were hot rolled at multiple passes into 0.06 to 0.20" thickness sheets.
  • the cold rolling is optional, all the example book mold sheets were further cold rolled to 0.05" thickness.
  • the cold rolled sheets were solution heat treated at a temperature range from 493 to 532°C (920 to 990°F).
  • the sheets were cold water quenched to room temperature.
  • the stretching or cold working is optional, all the example sheets were stretched at 2 to 6%.
  • the stretched sheets were aged to T8 temper in the temperature range of 166°C (330°F) for 24 hours. Tensile properties were evaluated for T8 temper sheets.
  • Table 2 gives the sheet tensile properties in the T8 (aged) temper.
  • the 0.2% offset yield strength (TYS) and ultimate tensile strength (UTS) along rolling direction (L) were measured under ASTM B557 specification.
  • the substantially Zr-free alloy #1 has 4.3 ksi higher strength than Zr containing alloy #2.
  • the low Cu level second pair (#3 and #4) shows that the substantially Zr-free alloy (#3) has 1.1 ksi higher strength than #2.
  • Example 1 Based on “Example 1" lab scale investigation on the role of Zr on the strength property was investigated.
  • Six industrial scale 406mm (16") thick ingots of Al-Li alloys were cast by DC (Direct Chill) casting process and produced to 0.05" to 0.11" thickness sheets.
  • the substantially Zr- free alloys with the non-intentionally added Zr levels in the industrial scale example ingots reflect the normal industrial practice.
  • Table 3 gives the chemical compositions of these industrial scale ingots.
  • Three lots (115565B4, 115733B8 and 115654B6) were inventive alloys. The other three alloys are not inventive alloys due to different Zr, Ag and Cu contents.
  • the Lot 638309A5 is AA2198 alloy, which was used as a baseline alloy of Al-Li sheet product.
  • the ingots were homogenized at temperatures from 496 to 538°C (925 to 1000°F).
  • the hot rolling temperatures were from 371 to 466°C (700 to 870°F).
  • the ingots were hot rolled at multiple passes into 0.06 to 0.20" thickness.
  • the cold rolling is optional, all sheets were further cold rolled to 0.108", 0.085", 0.05", and 0.025" thickness.
  • the cold rolled sheets were solution heat treated at a temperature range from 493 to 532°C (920 to 990°F).
  • the sheets were cold water quenched to room temperature.
  • the stretching or cold working is optional, all example sheets were stretched by 2 to 7%.
  • the stretched sheets without artificial aging were used for T3 temper tensile and formability evaluations.
  • the stretched sheets were further aged to T8 temper for strength, fracture, and fatigue performance evaluation.
  • the aging temperature was from 166°C (330°F) to 171°C (340°F) for 14 to 32 hours.
  • T3 temper sheet or coil The most critical performance for T3 temper sheet or coil is formability since the T3 temper sheet or coil will be formed first into the parts with different profiles and then artificially aged to the T8 temper for service application.
  • the formability was evaluated by both standard uniaxial bend and Forming Limit Diagram (FLD) tests.
  • FIG. 1 and 2 show the Forming Limit Diagrams (FLD), at respectively 0.05" and about 0.1" thickness of Invention and Non-Invention sheets.
  • FLD Forming Limit Diagrams
  • the FLD was evaluated based on ASTM E2218-02 (Reapproved 2008) specification.
  • a Forming Limit Curve (FLC) was generated by the points identified by necking on the samples.
  • the invention alloy sheet 115733B8 has better formability (higher critical major strain) than non-invention alloy sheet 115713B0 for all forming conditions. This observation is true for higher gage range (0.09" to 0.1"), the invention alloy sheet 115565B4 has better formability (higher critical major strain) than non-invention alloy sheet 115702B0 although the advantage is stronger at some conditions than other conditions.
  • the T3 temper sheet bending performance was also evaluated based on ASTM 290-09.
  • One end of the sheet specimen along with the bend support die was held together in a vise.
  • a force was applied on the other end of the sheet to bend against the radius of a support die to 180°.
  • the surface of the specimen was examined to determine if there were cracks.
  • the bend ratio R/t i.e. support die radius (R) to sheet thickness (t), is normally used to evaluate bending performance. The lower the bend ratio indicates the better the bending performance.
  • Table 4 gives the bending performance of Ag free low cost alloy sheets in T3 temper.
  • the invention alloy sheets have better bending formability. This observation is the same as those on previous FLD evaluation results.
  • the L direction normally has a lower bend ratio without surface cracking. The lower ratio represents better bending performance.
  • the invention alloy sheets have better bending performance than non-invention alloy sheets.
  • the inventive alloys have better bending performance than the widely used 2024 T3 sheets, where the minimum bending ratio required by the industry specification AMS 4037 is 2.5t.
  • Table 4 Bending performance of Ag free low cost alloy sheets in T3 temper Gage, in Invention Alloy?
  • Density is another critical factor for aerospace application.
  • the invention alloys advantages become more apparent when both density and formability are considered together.
  • FIG. 3 and 4 give the comparison of the combination of density and bending performance between Ag free low cost invention alloy and non-invention alloys sheets.
  • the invention alloy sheets have both lower density and lower minimum bend ratio compared with non-invention alloy sheets.
  • the tensile properties of T3 temper sheets along rolling direction (L), long transverse direction (LT) and 45 degree off the rolling direction (L45) are given in Table 5.
  • the invention alloy sheets have higher strength than existing T3 temper 2198 alloy sheet and also 2024-T3 minimum per AMS4037.
  • the difference of strength in different tensile orientations, L, LT and L45, (i.e. the in-plane anisotropy) is also very low for the invention alloy.
  • Table 6 and FIG. 5 give the tensile properties in the LT orientation for different aging times at 330°F (165.6 °C) .
  • the inventive alloy sheets have much higher strength than existing 2198 baseline alloy sheet for all the aging times.
  • the Ag free invention alloy sheets have both lower density and lower minimum bend ratio compared with the non-invention Ag free alloy sheets.
  • Table 6 The LT tensile properties at different aging times under 330F (165.6 °C) aging temperature Invention Alloy?
  • the specific aging practice was selected depending on alloy and gage.
  • the comprehensive characterization including strength in-plane anisotropy, corrosion resistance, fracture toughness, and fatigue resistance performance were conducted and disclosed in the present patent application.
  • Table 7 gives the tensile properties along L, LT, and L45 orientations for the different alloys and gages.
  • the inventive alloy sheets have much higher strength than the baseline 2198 alloy (638309A5).
  • the strengths of invention alloy sheets are slightly lower than those of non-invention alloy sheets 115702B3 and 115713B0.
  • the Ag free invention alloy sheets have both lower density and lower minimum bend ratio compared with non-invention Ag free alloy sheets 115713B0 and 115702B3.
  • the distinctiveness of the invention alloy can be demonstrated in the FIG. 6 and 7 which represent the combination of specific tensile yield strength (TYS) and minimum bend ratio in L and LT directions respectively.
  • the minimum LT bend ratio of present inventive alloy sheets can be less than "24.30-0.0292* "Specific LT TYS”", and the minimum L bend ratio of present alloy sheet can be less than "13.11 - 0.0146* "Specific L TYS””.
  • the minimum LT bend ratio is less than "23.65-0.0292 * "Specific LT TYS””
  • the minimum L bend ratio is less than "12.88 - 0.0146 * "Specific L TYS””.
  • the specific strength equals the strength divided by density.
  • the unit of specific strength is "ksi/(lb/in 3 )".
  • Corrosion resistance is a key design consideration for airframe manufacturers.
  • the MASTMASSIS test is generally considered to be a good representative accelerated corrosion test method for Al-Li based alloys.
  • the MASTMASSIS test was based on ASTM G85-11 Annex-2 under dry-bottom conditions.
  • the sample size was 2.0" L x 2.0" LT at middle of sheet thickness.
  • the temperature of the exposure chamber through the duration of the test was 49 ⁇ 2°C.
  • FIG. 8 is a picture of typical surface images after 72 hours and 672 hours MASTMASSIS testing exposure times. The surfaces are very clean and shiny. No exfoliation is evident for all the exposure times. The excellent corrosion resistance of pitting/EA can be concluded for all exposure times.
  • FIG. 9 is a graph showing the da/dN as a function of stress intensity factor of all Ag free inventive and non-inventive alloys sheets in T8 temper.
  • the testing condition includes L-T orientation, stress ratio of 0.1 and a frequency of 10Hz. It is interesting to observe that all sheets have similar fatigue crack growth resistance performance although the invention alloy sheets (115654B6, 115733B8, 115565B4) have lower density and better formability than non-invention alloy sheets (115713B0,115702B3).
  • invention alloy The excellent fatigue crack growth resistance of invention alloy can be demonstrated in FIG. 10 .
  • the 7075-T6 data is from ASM Handbook.
  • the invention alloy sheets have much slower fatigue crack growth rate (daldN) than commonly used 7075-T6 sheet.
  • FIG. 11 is a graph showing the effective crack resistance KR eff as function of effective crack extension (Da eff ) of Al-Li sheets. All Al-Li sheets were tested in the T8 temper and the L-T orientation.
  • the inventive alloy sheets (115654B6 and 115733B8) have similar fracture toughness as non-invention alloy sheets (115713B0 and 115702B3). It should be mentioned that the inventive alloy sheets (115654B6, 115733B8) have lower density and better formability than non-invention alloy sheets (115713B0 and 115702B3).
  • Example 2 Full Industrial Scale Examples demonstrates that the distinct and unique chemical compositions (no Ag, substantially Zr-free, and combination of Cu, Li, Mg, Mn, and Zn) of present invention alloy can provide superior formability, low density, and excellent strength, corrosion resistance, fracture toughness and fatigue crack growth resistance of Al-Li sheet products.
  • FIG. 12 to 17 gives the grain structures of Al-Li sheets. It is well known that the grain structure is strongly affected by sheet gage. Therefore, the comparison of microstructure is gage dependent.
  • the invention alloy sheet 115565B4 has finer and a more equi-axed grain structure than the non-invention alloy sheet 115702B3.
  • the present invention alloy sheet 115713B0 has much finer, equi-axed grain structure than the non-invention alloy sheets 115713B0 and 638309A5.
  • the invention alloy 115654B6 a very fined, equi-axed grain structure was clearly observed.
  • the ideal grain structures of the invention alloy sheets are attributed mainly to the unique substantially Zr-free chemical composition along with the unique combination of Cu, Li, Mn, and Mg.
  • the crystallographic texture strongly affects final product properties, especially formability.
  • a Rigaku D/Max X-Ray diffractometer was used to measure the T3 temper sheet textures.
  • the alpha rotation angle was from 15° to 90°, and alpha step angle was 5° by the Schulz back-reflection method using CuK ⁇ radiation.
  • Table 8 summarizes the main texture components and their volume fractions of T3 temper sheets at T/4 (quarter thickness) and T/2 (middle thickness) locations. It is well established that texture is strongly related to final sheet thickness.
  • the non-invention alloy sheets (115713B8 and 115702B3) have very typical rolling textures - very strong Brass and S textures "hard” components.
  • the invention alloy sheets (115565B4 and 115733B8) have very strong Cube and R-Cube "soft” textures.
  • the ratios of "Soft” to "Hard” texture components were given in FIG. 18 and 19 for two sheet thicknesses.
  • invention alloy sheets have much higher ratios of "Soft” to “Hard” texture components than non-invention alloy sheets. Since the processing practices were the same for the invention and non-invention alloy sheets, such distinctive texture differences can be attributed to the lack of Zr and the combination of other elements such as Cu, Li, Mg, Mn.
  • the distinctiveness of crystallographic texture in terms of the ratio of "Soft” to “Hard” texture components can be further demonstrated in FIG. 20 and 21 for Th/4 and Th/2 respectively.
  • the minimum ratios for intention alloy are higher than "0.75 - 0.5 * gage” and "0.85 - 5.0 * gage” at sheet quarter thickness (th/4) and center thickness (th/2) respectively.
  • the preferred ratios are higher than "0.83 - 0.5 * gage” and "0.98 - 5.0 * gage” at th/4 and th/2 respectively for invention alloys.
  • the more preferred ratios are higher than "0.9 - 0.5 * gage” and "1.1 - 5.0 * gage” at th/4 and th/2 respectively for invention alloys.
  • the unit of the gage is inch.
  • Table 8 Texture components and their volume fractions of T3 temper sheets at T/4 (quarter thickness) and T/2 (middle thickness) locations Sample ID Inventio n Alloy? Gage, in Location Cube Goss Brass S Copper R-Cube "Soft” / "Hard” % % % % % % 115733B8 Yes 0.05 T/4 6.35 2.30 5.62 7.63 3.53 5.96 0.929 T/2 6.75 2.33 5.28 8.46 4.34 5.82 0.915 11571388 No 0.05 T/4 5.63 2.36 6.92 9.31 3.80 5.01 0.656 T/2 5.05 2.56 10.36 11.87 3.61 4.49 0.429 115565B4 Yes 0.108 T/4 6.54 2.28 5.48 7.69 3.75 5.31 0.900 T/2 5.18 2.36 7.85 8.30 2.91 4.93 0.626 115702B3 No 0.085 T/4 5.39 2.46 7.94 8.58 3.71 4.55 0.602 T/2 4.09 2.40 13.84 11.64 2.77 3.74 0.307

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Claims (14)

  1. Kostengünstige, im Wesentlichen Zr-freie Al-Li-Legierung mit hoher Verformbarkeit, die Folgendes umfasst: von 3,2 bis 4,1 Gew.-% Cu, von 1,0 bis 1,8 Gew.-% Li, von 0,8 bis 1,2 Gew.-% Mg, von 0,10 bis 0,50 Gew.-% Zn, von 0,1 bis 1,0 Gew.-% Mn, weniger als 0,1 Gew.-% Ag, weniger als 0,05 Gew.-% Zr, bis zu 0,15 Gew.-% Ti, bis zu 0,12 Gew.-% Si, bis zu 0,15 Gew.-% Fe,
    bis zu 0,15 Gew.-% von jedem zufälligen Begleitelement, wobei diese zufälligen Begleitelemente insgesamt 0,35 Gew.-% nicht übersteigen,
    wobei der Rest Aluminium ist und
    wobei der Mg-Gehalt mindestens gleich oder höher ist als das Zweifache an Zn in Gewichtsprozent.
  2. Aluminium-Lithium-Legierung nach Anspruch 1, die 3,4 bis 3,9 Gew.-% Cu umfasst; und /oder
    1,1 bis 1,7 Gew.-% Li umfasst; und /oder
    0,20 bis 0,50 Gew.-% Zn umfasst; und /oder
    0,2 bis 0,6 Gew.-% Mn umfasst.
  3. Aluminium-Lithium-Legierung nach Anspruch 1 oder 2, die maximal 0,05 Gew.% Ag umfasst; und/oder
    maximal 0,01 Gew.-% Ag umfasst.
  4. Aluminium-Lithium-Legierung nach einem der Ansprüche 1-3, die maximal 0,05 Gew.-% Si umfasst; und/oder
    maximal 0,08 Gew.-% Fe umfasst.
  5. Aluminium-Lithium-Legierung nach Anspruch 1, die Folgendes umfasst: von 3,4 bis 3,9 Gew.-% Cu, von 1,1 bis 1,7 Gew.-% Li, von 0,8 bis 1,2 Gew.-% Mg, von 0,20 bis 0,50 Gew.-% Zn, von 0,20 bis 0,6 Gew.-% Mn, weniger als 0,05 Gew.-% Ag, weniger als 0,05 Gew.-% Zr, bis zu 0,15 Gew.-% Ti, bis zu 0,05 Gew.-% Si, bis zu 0,08 Gew.-% Fe,
    bis zu 0,15 Gew.-% von jedem zufälligen Begleitelement, wobei diese zufälligen Begleitelemente insgesamt 0,35 Gew.-% nicht übersteigen,
    wobei der Rest Aluminium ist und
    wobei der Mg-Gehalt mindestens gleich oder höher ist als das Zweifache an Zn in Gewichtsprozent.
  6. Aluminium-Lithium-Legierung nach einem der Ansprüche 1 bis 5, wobei die Aluminium-Lithium-Legierung in Form eines gewalzten, extrudierten oder geschmiedeten Produkts von 0,254 mm (0,01 ") bis 6,325 mm (0,249") Dicke vorliegt; wobei optional die Aluminium-Lithium-Legierung eine Dicke von 0,254 mm (0,01 ") bis 3,175 mm (0,125") aufweist.
  7. Aluminium-Lithium-Legierung nach einem der Ansprüche 1 bis 5, wobei die Aluminium-Lithium-Legierung in Form einer Platte oder einer Spule vorliegt, die eine Dicke von 0,254 mm (0,01 ") bis 6,325 mm (0,249") aufweisen;
    wobei optional die Aluminium-Lithium-Legierung eine Dicke von 0,254 mm (0,01 ") bis 3,175 mm (0,125") aufweist.
  8. Gewalztes Produkt, das eine Aluminium-Lithium-Legierung nach einem der Ansprüche 1 bis 7 umfasst, das eine Dicke von 0,254 mm (0,01 ") bis 6,325 mm (0,249") aufweist, in einem lösungsgeglühten, abgeschreckten und gestreckten Zustand ein Verhältnis von "weicher" zu "harter" Textur von höher als "0,75-0,5 ∗ Gauge" und "0,9-0,5 ∗ Gauge" bei einem Viertel der Plattendicke (th/4) bzw. bei mittlerer Plattendicke (th/2) zeigt, wobei die Einheit von Gauge Zoll ist; oder
    eine Dicke von 0,254 mm (0,01 ") bis 6,325 mm (0,249") aufweist, in einem lösungsgeglühten, abgeschreckten und gestreckten Zustand ein Verhältnis von "weicher" zu "harter" Textur von höher als "0,8-0,5 ∗ Gauge" und "1,0-5,0 ∗ Gauge" bei einem Viertel der Plattendicke (th/4) bzw. bei mittlerer Plattendicke (th/2) zeigt, wobei die Einheit von Gauge Zoll ist; oder
    eine Dicke von 0,254 mm (0,01 ") bis 6,325 mm (0,249") aufweist, in einem lösungsgeglühten, abgeschreckten und gestreckten Zustand ein Verhältnis von "weicher" zu "harter" Textur von höher als "0,9-0,5 ∗ Gauge" und "1,1-5,0 ∗ Gauge" bei einem Viertel der Plattendicke (th/4) bzw. bei mittlerer Plattendicke (th/2) zeigt, wobei die Einheit von Gauge Zoll ist;
    wobei die Volumenfraktionen von Texturkomponenten durch Röntgendiffraktometrie beurteilt werden; und wobei Messing- und S-Texturen "harte" Texturen sind und Würfel- und R-Würfel- "weiche" Texturen sind.
  9. Gewalztes Produkt, das eine Aluminium-Lithium-Legierung nach einem der Ansprüche 1 bis 7 umfasst, das eine Dicke von 0,254 mm (0,01") bis 6,325 mm (0,249") aufweist, in einem lösungsgeglühten, abgeschreckten, gestreckten und künstlich gealterten Zustand ein minimales LT-Biegungsverhältnis von weniger als "24,30-0,0292 ∗ "Spezifische LT TYSʺʺ und ein minimales L-Biegungsverhältnis von weniger als "13,11-0,0146 ∗ "Spezifische L TYSʺʺ zeigt, wobei die Einheit von spezifischer Festigkeit "ksi/(lb/in3)" ("ksi/(Pfund/Zoll3") ist; oder
    eine Dicke von 0,254 mm (0,01") bis 6,325 mm (0,249") aufweist, in einem lösungsgeglühten, abgeschreckten, gestreckten und künstlich gealterten Zustand ein minimales LT-Biegungsverhältnis von weniger als "23,65-0,0292 ∗ "Spezifische LT TYSʺʺ und ein minimales L-Biegungsverhältnis von weniger als "12,88-0,0146 ∗ "Spezifische L TYSʺʺ zeigt, wobei die Einheit von spezifischer Festigkeit "ksi/(lb/in3)" ist; oder
    wobei TYS die Zugfestigkeit ist und "Spezifische L TYS" die längsgerichtete Zugfestigkeit durch Dichte ist.
  10. Gewalztes Produkt nach Anspruch 8 oder 9, wobei die Aluminium-Lithium-Legierung in Form einer Platte oder einer Spule vorliegt, die eine Dicke von 0,254 mm (0,01") bis 3,175 mm (0,125") aufweisen.
  11. Verfahren zur Herstellung einer hochfesten, kostengünstigen Aluminium-Lithium-Legierung mit hoher Verformbarkeit, wobei das Verfahren Folgendes umfasst:
    a. Gießen eines Guts eines Barrens aus Aluminiumlegierung, der die Aluminium-Lithium-Legierung nach einem der Ansprüche 1-10 umfasst, zur Herstellung eines Abgusses;
    b. Homogenisieren des Abgusses zur Herstellung eines homogenisierten Abgusses;
    c. Warmbearbeiten des homogenisierten Abgusses durch ein oder mehrere Verfahren, die aus der Gruppe ausgewählt sind, die aus Walzen, Extrusion und Schmieden besteht, zur Ausbildung eines bearbeiteten Guts;
    d. optional Kaltwalzen des bearbeiteten Guts;
    e. Lösungsglühen (SHT) des optional kaltgewalzten, bearbeiteten Guts zur Herstellung eines SHT-Guts;
    f. Abschrecken des SHT-Guts mit kaltem Wasser, um ein mit kaltem Wasser abgeschrecktes SHT-Gut herzustellen;
    g. optional Strecken des mit kaltem Wasser abgeschreckten SHT-Guts; und
    h. künstliche Alterung des mit kaltem Wasser abgeschreckten, optional gestreckten SHT-Guts.
  12. Verfahren nach Anspruch 11, wobei der Schritt des Homogenisierens das Homogenisieren bei Temperaturen von 454 bis 549 °C (850 bis 1020 °F) einschließt; und/oder
    wobei der Schritt des Warmbearbeitens das Warmwalzen bei einer Temperatur von 343 bis 499 °C (650 bis 930 °F) einschließt; und/oder
    wobei der Schritt des optionalen Kaltbearbeitens eine Kaltreduzierung bei 20 % bis 95 % einschließt; und/oder
    wobei der Schritt des Lösungsglühens ein Lösungsglühen bei einem Temperaturbereich von 454 bis 543 °C (850 bis 1010 °F) einschließt; und/oder
    wobei der Schritt des optionalen Streckens das Strecken bis zu 15 % einschließt; und/oder
    wobei der Schritt der Alterung 121 bis 205 °C (250 bis 400 °F) einschließt und die Alterungszeit in dem Bereich von 2 bis 60 Stunden liegen kann.
  13. Aluminium-Lithium-Legierung nach Anspruch 1, die Folgendes umfasst: von 3,4 bis 3,9 Gew.-% Cu, von 1,1 bis 1,7 Gew.-% Li, von 0,8 bis 1,2 Gew.-% Mg, von 0,20 bis 0,50 Gew.-% Zn, von 0,20 bis 0,6 Gew.-% Mn, weniger als 0,05 Gew.-% Ag, weniger als 0,05 Gew.-% Zr, bis zu 0,15 Gew.-% Ti, bis zu 0,05 Gew.-% Si, bis zu 0,08 Gew.-% Fe,
    bis zu 0,15 Gew.-% von jedem zufälligen Begleitelement, wobei diese zufälligen Begleitelemente insgesamt 0,35 Gew.-% nicht übersteigen,
    wobei der Rest Aluminium ist und
    wobei der Mg-Gehalt mindestens gleich oder höher ist als das Zweifache an Zn in Gewichtsprozent; und
    wobei die Aluminium-Lithium-Legierung ein gewalztes Legierungsprodukt ist, das eine Dicke von 0,254 mm (0,01") bis 6,325 mm (0,249") aufweist.
  14. Aluminium-Lithium-Legierung nach Anspruch 13, wobei die Aluminium-Lithium-Legierung eine Dicke von 0,254 mm (0,01") bis 3,175 mm (0,125") aufweist.
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CN115927934B (zh) * 2022-07-01 2024-01-26 湖北汽车工业学院 一种具有{001}＜x10＞织构的Al-Cu铸造合金及其制备方法和应用

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