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WO2022270483A1 - Agent de prévention de fragilisation par l'hydrogène pour matériau en alliage d'aluminium - Google Patents

Agent de prévention de fragilisation par l'hydrogène pour matériau en alliage d'aluminium Download PDF

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WO2022270483A1
WO2022270483A1 PCT/JP2022/024630 JP2022024630W WO2022270483A1 WO 2022270483 A1 WO2022270483 A1 WO 2022270483A1 JP 2022024630 W JP2022024630 W JP 2022024630W WO 2022270483 A1 WO2022270483 A1 WO 2022270483A1
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particles
aluminum alloy
alloy material
hydrogen embrittlement
hydrogen
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PCT/JP2022/024630
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English (en)
Japanese (ja)
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一行 清水
裕之 戸田
正剛 山口
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国立大学法人岩手大学
国立大学法人九州大学
国立研究開発法人日本原子力研究開発機構
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Priority to JP2023530471A priority Critical patent/JPWO2022270483A1/ja
Publication of WO2022270483A1 publication Critical patent/WO2022270483A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent

Definitions

  • the present invention relates to a hydrogen embrittlement inhibitor for aluminum alloy materials.
  • Patent Document 1 contains Zn5.0 to 7.0%, Mg1.0 to 3.0%, Cu1.0 to 3.0%, and Cr0.05 to 0.3%, Zr0.05 to One or more selected from 0.25%, Mn 0.05 to 0.40%, and Sc 0.05 to 0.35% in a total amount within the range of 0.05 to 0.5% Further, using an Al-Zn-Mg-Cu-based aluminum alloy containing Si as impurities of 0.25% or less and Fe as impurities of 0.25% or less and the balance being Al and other inevitable impurities, After homogenizing the ingot by holding it at a temperature within the range of 450 to 520 ° C for 1 hour or more, in the process of cooling the ingot, the average cooling rate to at least 400 ° C.
  • Patent Document 2 contains 4.5 to 8.5 wt% Zn, 1.5 to 3.5 wt% Mg, and 0.8 to 2.6 wt% Cu, and further contains at least one of Mn, Cr, Zr, V, and Ti.
  • the Fe content in the alloy is restricted to 0.15 wt% or less to prevent corrosion cracking.
  • Patent Document 3 Zn5 to 8 wt%, Mg1.2 to 4.0 wt%, Cu1.5 wt% to 4.0 wt%, Ag0.03 to 1.0 wt%, Fe0.01 to 1.0% by weight, Ti 0.005-0.2% by weight, V 0.01-0.2% by weight, and Mn 0.01-1.5% by weight, Cr 0.01-0.6% by weight , Zr 0.01 to 0.25% by weight, B 0.0001 to 0.08% by weight, and Mo 0.03 to 0.5% by weight, with the remainder consisting of aluminum and unavoidable impurities
  • a high-strength aluminum alloy for welded structures with excellent resistance to stress corrosion cracking is described.
  • Non-Patent Document 1 describes the hydrogen trapping in aluminum and the hydrogen embrittlement fracture mechanism due to intergranular/quasi-cleavage fracture, and describes the possibility of hydrogen trapping in precipitates.
  • JP 2011-058047 A Japanese Patent Publication No. 1-025386 Patent No. 2915487
  • Non-Patent Document 1 did not specify a specific composition of the precipitate.
  • the problem to be solved by the present invention is to provide a hydrogen embrittlement inhibitor for aluminum alloy materials that can effectively prevent or suppress hydrogen embrittlement.
  • a hydrogen embrittlement inhibitor for an aluminum alloy material that can prevent hydrogen embrittlement of an aluminum alloy material and is used to be contained as second phase particles inside the aluminum alloy material, wherein the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al 7 Cr particles, Al 9 Mn 4
  • a hydrogen embrittlement inhibitor for an aluminum alloy material comprising at least one of particles, Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles.
  • a hydrogen embrittlement inhibitor for an aluminum alloy material that can prevent hydrogen embrittlement of an aluminum alloy material and is used to be contained as second phase particles inside the aluminum alloy material, wherein the second phase particles are , Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles and Al 2 Ca particles, Hydrogen embrittlement inhibitor for aluminum alloy materials.
  • the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Ti particles, Al 3 Sc particles, Al 9 Mn 4 particles, and Al 12 Mn.
  • the second phase particles include at least one of Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Ti particles and Al 3 Sc particles.
  • the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 3 Ti particles, Al 3 Sc particles, Al 9 Mn 4 particles, Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles
  • Second-phase particles include at least one of Sn particles, Al 11 Mn 3 Zn 2 particles, Al 3 Ti particles, and Al 3 Sc particles [1] to [4], [1- A hydrogen embrittlement inhibitor for an aluminum alloy material according to any one of 1] and [3-1].
  • FIGS. 1(a) to 1(e) are virtual cross sections of the interior of each aluminum alloy material observed by synchrotron radiation nanotomography.
  • FIG. 1(a) is a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Sc) of Example 3.
  • FIG. 1(b) is a virtual cross section of a tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Zr) of Comparative Example 7.
  • FIG. FIG. 1(c) is a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Example 4 (the fourth element M is Mn).
  • FIG. 1(a) is a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Sc) of Example 3.
  • FIG. 1(b) is a virtual cross section of a tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Zr) of
  • FIG. 1(d) is a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Cr) of Comparative Example 8.
  • FIG. 1(e) is a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material (the fourth element M is Ni) of Comparative Example 6.
  • FIG. 2(a) is a fracture surface of the aluminum alloy material (Std.: no fourth element M) of Comparative Example 1 after the tensile test.
  • FIG. 2(b) is a fracture surface of the aluminum alloy material (the fourth element M is Zr) of Comparative Example 7 after the tensile test.
  • FIG. 2(c) is a fracture surface of the aluminum alloy material (the fourth element M is Cr) of Comparative Example 8 after the tensile test.
  • FIG. 2(d) is a fracture surface of the aluminum alloy material (the fourth element M is Sc) of Example 3 after the tensile test.
  • FIG. 2(e) is a fracture surface of the aluminum alloy material (the fourth element M is Mn) of Example 4 after the tensile test.
  • FIG. 2(f) is a fracture surface of the aluminum alloy material (the fourth element M is Ti) of Example 1 after the tensile test.
  • FIG. 2(g) is a fracture surface of the aluminum alloy material (the fourth element M is Ni) of Comparative Example 6 after the tensile test.
  • FIG. 3 is a bar graph showing the area ratio of hydrogen embrittlement fracture (quasi-cleavage fracture and intergranular fracture) on the fracture surface of the aluminum alloy material of each example, each comparative example, and reference example 1 after the tensile test.
  • FIG. 4 is a line graph showing the reduction of area of the aluminum alloy materials of each example, each comparative example, and reference example 1 after the tensile test.
  • FIG. 5(a) is a schematic diagram of the crystal structure of the Al 3 Sc particles formed in Example 3 and its hydrogen trap sites.
  • FIG. 5(b) is a schematic diagram of the crystal structure of the Al 3 Ti particles formed in Example 1 and its hydrogen trap sites.
  • FIG. 5(c) is a schematic diagram of the crystal structure of the Al 6 Mn particles formed in Example 4 and its hydrogen trap sites.
  • FIG. 5(d) is a schematic diagram of the crystal structure of Al 9 Mn 4 particles.
  • FIG. 5(e) is a schematic diagram of the crystal structure of Al 12 Mn 3 Si particles.
  • FIG. 5(f) is a schematic diagram of the crystal structure of Al 31 Mn 6 Cu 2 particles.
  • FIG. 6 is a number line diagram of the hydrogen trap energy of each microstructure in an aluminum alloy material.
  • FIG. 7 is a plot diagram of the relationship between the maximum hydrogen trap energy inside the particle and the quasi-cleavage fracture area ratio.
  • FIG. 8A is a schematic diagram of the crystal structure of Al 3 Y particles and their hydrogen trap sites.
  • FIG. 8B is a schematic diagram of the crystal structure of Al 2 Ca particles and their hydrogen trap sites.
  • FIG. 8(c) is a schematic diagram of the crystal structure of Al 7 Cr particles and their hydrogen trap sites.
  • the hydrogen embrittlement inhibitor for aluminum alloy materials of the present invention can prevent hydrogen embrittlement of aluminum alloy materials, and is used to be contained as second phase particles inside aluminum alloy materials.
  • the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al7Cr particles, Al9Mn4 particles , Al12Mn3Si particles and Al31Mn6Cu2 particles .
  • This configuration can effectively prevent or suppress hydrogen embrittlement of the aluminum alloy material.
  • hydrogen embrittlement can be sufficiently effectively prevented or suppressed at the level required for the aircraft and space industries.
  • the hydrogen embrittlement inhibitor for an aluminum alloy material of the present invention includes Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, and Al having the above hydrogen trap sites. 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al 7 Cr particles, Al 9 Mn 4 particles, Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles. Hydrogen embrittlement cracking includes intergranular cracking and quasi-cleavage cracking. In the present invention, it is preferable that quasi-cleavage cracking can be effectively prevented or suppressed, and intergranular cracking and quasi-cleavage cracking can be effectively prevented or suppressed. Preferred embodiments of the present invention are described below.
  • the raw aluminum alloy material to be prevented from hydrogen embrittlement may be a new aluminum alloy material or an existing aluminum alloy material.
  • the hydrogen embrittlement inhibitor for aluminum alloy materials of the present invention is preferably capable of preventing hydrogen embrittlement of aluminum alloy materials of existing alloys within the JIS standard (JIS H 4000:2014, etc.) and/or new alloys outside the JIS standard.
  • the raw aluminum alloy material contains aluminum as a main component, and preferably contains 50% by mass or more of aluminum.
  • a preferred aspect of the raw aluminum alloy material is a pure aluminum alloy with a purity of 99.0% or more. Examples of pure aluminum alloys include 1000 series alloys such as A1050, A1100 and A1200.
  • the raw aluminum alloy material it preferably contains at least Cu.
  • Al--Cu alloys include 2000 series alloys such as A2017 and A2024.
  • it preferably contains at least Mn.
  • Al--Mn alloys include, for example, 3000 series alloys such as A3003, A3004 and A3005.
  • it preferably contains at least Si.
  • Al—Si alloys include 4000 series alloys such as A4042, A4043 and A4343.
  • Examples of Al--Mg alloys include 5000 series alloys such as A5005, A5052, A5083 and A5182.
  • the raw aluminum alloy material it preferably contains at least Mg and Si.
  • Al--Mg--Si alloys include 6000 series alloys such as A6061 and A6063.
  • it preferably contains at least Zn and Mg.
  • Al--Zn--Mg alloys include 7000 series alloys such as A7075 and A7050 alloys.
  • the aluminum alloy material is preferably an Al--Zn--Mg alloy containing at least Zn and Mg.
  • Al--Zn--Mg alloys are alloys with the highest strength among wrought aluminum alloys for practical use, and are used in transportation equipment such as bullet trains and aircraft. This is because the strength of this alloy system is currently rate-determined by hydrogen embrittlement.
  • the alloy composition of the aluminum alloy material obtained by adding the hydrogen embrittlement inhibitor of the aluminum alloy material of the present invention to the raw material aluminum alloy material is mainly composed of aluminum, and aluminum is 50% by mass. It is preferable to include the above.
  • the preferred range of the alloy composition of such an aluminum alloy material is the range of the composition in which the hydrogen embrittlement inhibitor of the aluminum alloy material of the present invention is added in a preferred amount to the preferred aluminum alloy material of the raw material. .
  • the shape of the aluminum alloy material is not particularly limited.
  • the aluminum alloy material may be in the form of lumps or particles, preferably in the form of lumps.
  • the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al7Cr particles, Al9Mn4 particles , Al12Mn3Si particles and Al31Mn6Cu2 particles .
  • Second phase particles refer to particles having a composition different from that of the mother phase.
  • the second phase particles of the aluminum alloy material are particles of a composition different from that of Al or its aluminum alloy material.
  • the second phase grains should have higher hydrogen trap energies than the coherent precipitate interfaces.
  • the hydrogen trapping energy of the second phase particles should be at least higher than 0.35 eV/atom at the coherent precipitate interface.
  • the second phase grains having a higher hydrogen trapping energy than the coherent precipitate interface.
  • First-principles calculations can determine second-phase grains that have higher hydrogen trap energies than the coherent precipitate interface. The first-principles calculation is to express the electronic state theoretically by mathematically solving the Schrödinger equation (without using experimental data or empirical parameters). The distribution of hydrogen at each trap site can be calculated from the density of other hydrogen trap sites such as grain boundaries, precipitates, interstitial spaces, and the binding energy with hydrogen.
  • the hydrogen trap energy of the second phase particles is preferably 0.40 eV/atom or more, more preferably 0.45 eV/atom or more, particularly preferably 0.50 eV/atom or more, and is semi-consistent More particularly preferred is higher than 0.55 eV of the precipitate interface.
  • the second phase particles are Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Ti particles, Al 3 Sc particles, Al 9 Mn 4 particles, Al 12 It preferably contains at least one of Mn3Si particles and Al31Mn6Cu2 particles, and includes Sn particles, Al11Mn3Zn2 particles , Al3Ti particles , Al3Sc particles , Al9Mn4 particles , More preferably, at least one of Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles is included.
  • Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al 7 Cr particles, Al 9Mn4 particles , Al12Mn3Si particles and Al31Mn6Cu2 particles are particles in which the atomic ratio of each element other than Al deviates from the stoichiometric composition by within 20%. More preferably, the particles deviate within 10% from the stoichiometric composition, and most preferably, the particles deviate within 1% from the stoichiometric composition.
  • Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al 7 Cr particles, Al 9 Mn 4 particles, Al 12 Mn 3 Si particles, and Al 31 Mn 6 Cu 2 particles can be expected to have similar effects even if they are particles in which a trace element is solid-dissolved in addition to each element constituting each particle.
  • the particles in which trace elements are solid - dissolved are also the Sn particles and the Al11Mn3Zn2 particles of the present invention.
  • the particles are preferably solid-dissolved particles, more preferably 10 mol % or less solid-dissolved particles, and particularly preferably 1 mol % or less solid-dissolved particles.
  • Al 9 Co 2 particles may be particles composed of Al—Co—Mn—Mg, and such particles are included in the Al 9 Co 2 particles of the present invention.
  • each trace element (For example, Mn element or Mg element) is independently preferably 30 mol % or less, more preferably 10 mol % or less, and particularly preferably 1 mol % or less relative to Al element.
  • each trace element (for example, the total of Mn element and Mg element) is also preferably 30 mol% or less, more preferably 10 mol% or less, and 1 mol% or less with respect to Al element. is particularly preferred.
  • Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, Al 2 Ca particles, Al 7 The atomic ratio of each element other than Al that constitutes each of the Cr particles, Al 9 Mn 4 particles, Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles deviates within 30% from the stoichiometric composition, and A similar effect can be expected for particles in which a trace element is dissolved in addition to each element constituting each particle.
  • the shape of the second phase particles includes various shapes such as spherical, ellipsoidal, prismatic, cylindrical, cubic, cuboid, and scale-like, preferably spherical or ellipsoidal.
  • the volume fraction of the second phase particles is preferably 0.05 to 10.0%, more preferably 0.1 to 5.0%, particularly 0.5 to 2.0%. preferable.
  • the volume ratio of the second phase particles can be calculated as the volume of the second phase particles with respect to the volume of the aluminum alloy material, for example, by 3D analysis using X-ray tomography (CT).
  • the number density of the second phase particles can be from 0.01 ⁇ 10 17 /m 3 to 100 ⁇ 10 17 /m 3 .
  • the number density of the second phase particles is preferably 0.1 ⁇ 10 17 /m 3 to 10 ⁇ 10 17 /m 3 , and 0.2 ⁇ 10 17 /m 3 to 5 ⁇ 10 17 /m 3 0.2 ⁇ 10 17 /m 3 to 3 ⁇ 10 17 /m 3 is particularly preferred.
  • the number density of the second-phase particles can be calculated, for example, by 3D analysis using high-resolution X-ray tomography (CT) with a spatial resolution of up to 1 ⁇ m.
  • CT high-resolution X-ray tomography
  • the average particle size of the second phase particles is preferably 0.1 to 20 ⁇ m.
  • the upper limit of the average particle size of the second phase particles is more preferably 10 ⁇ m or less, particularly preferably 5.0 ⁇ m or less. More preferably, the lower limit of the average particle size of the second phase particles is 0.5 ⁇ m or more.
  • the average particle size of the second phase particles can be calculated as an arithmetic average by 3D analysis using, for example, X-ray tomography (CT).
  • ⁇ Method for preventing hydrogen embrittlement of aluminum alloy material There are no particular restrictions on the method for preventing hydrogen embrittlement of aluminum alloy materials or the method for producing aluminum alloy materials. Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles, Al 3 Sc particles, and Al 2 Ca particles for the raw material aluminum alloy material , Al 7 Cr particles, Al 9 Mn 4 particles, Al 12 Mn 3 Si particles and Al 31 Mn 6 Cu 2 particles. , the hydrogen embrittlement of the aluminum alloy material can be prevented.
  • These 12 types of particles may be added to the raw aluminum alloy material, and elements (Sn, Co, Mn, Y, Ti, Sc, Ca, Cr) corresponding to these 12 types of particles may be added during production. , Si or Cu) may be added to form these 12 types of particles, and finally these 12 types of particles may be used as a hydrogen embrittlement inhibitor (in the case of Al 6 Mn particles, the raw material aluminum increasing the Mn concentration of the alloy material, etc.). No special manufacturing equipment or manufacturing conditions are required. These particles can be formed by thermomechanical treatment during alloy manufacture.
  • the raw material aluminum alloy material may be a raw material mixture before each metal including Al or a metal compound is alloyed.
  • An aluminum alloy material can be produced by known processes such as heat treatment, rolling, forging and/or casting of a raw material aluminum alloy material (which may be a mixture of raw materials).
  • a raw material aluminum alloy material which may be a mixture of raw materials.
  • elements Sn, Co, Mn, Y, Ti, Sc, Ca, Cr, Si or Cu
  • Sn particles Sn particles, Al 11 Mn 3 Zn 2 particles, Al 9 Co 2 particles, Al 6 Mn particles, Al 3 Y particles, Al 3 Ti particles
  • heat treatment, rolling, and forging may not be performed.
  • the chemical composition of Al-10.0Zn-1.06Mg-M corresponds to 12 types of particles during casting.
  • the amount of the fourth element to be added is preferably 0.05 to 5.00% by mass, more preferably 0.10 to 3.00% by mass, and more preferably 0.15 to 2.00% by mass. 50% by mass is particularly preferred.
  • An example of a more preferable range of the addition amount of the fourth element in this case is as follows.
  • the fourth element is Co, it is preferably 0.05 to 0.50% by mass, more preferably 0.10 to 0.30% by mass, and particularly preferably 0.15 to 0.25% by mass.
  • the fourth element is Sc, it is preferably 0.10 to 2.00% by mass, more preferably 0.50 to 1.50% by mass, and particularly preferably 0.80 to 1.00% by mass.
  • the fourth element is Ti, it is preferably 0.10 to 2.00% by mass, more preferably 0.50 to 1.50% by mass, and particularly preferably 0.90 to 1.10% by mass.
  • the fourth element is Mn, it is preferably 0.50 to 5.00% by mass, more preferably 1.00 to 3.00% by mass, particularly preferably 1.50 to 2.50% by mass, and 1.80 to 2.00% by mass is more particularly preferred.
  • An aluminum alloy material satisfying the chemical composition of Al-10.0Zn-1.06Mg-M (M is the fourth element) was prepared by the following method.
  • This aluminum alloy material is also an Al--Zn--Mg alloy containing 50% by mass or more of Al as the main component.
  • Table 1 below shows the addition amounts (unit: mass %) of the 13 types of the fourth element (M). This addition amount is adjusted so that the volume ratio of the compound formed in the aluminum is approximately the same.
  • the fourth element material was added to the smelter to form second phase particles inside the material. Specifically, heating at 500 ° C. for 24 hours (homogenization), heating at 450 ° C. (hot rolling), heating at 500 ° C. for 5 hours (solution treatment), heating at 120 ° C. for 40 hours and 180 ° C. for 7 hours. Overaging was performed. The obtained non-discharge-machined aluminum alloy material was subjected to underwater discharge machining (EDM) to prepare a test piece with an increased amount of hydrogen.
  • EDM underwater discharge machining
  • Figs. 1(a) to 1(e) show virtual cross sections of the inside of each aluminum alloy material observed by synchrotron radiation nanotomography.
  • Fig. 1(a) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Example 3 (the fourth element M is Sc).
  • Fig. 1(b) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Comparative Example 7 (where the fourth element M is Zr).
  • Fig. 1(a) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Comparative Example 7 (where the fourth element M is Zr).
  • FIG. 1(c) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Example 4 (where the fourth element M is Mn).
  • FIG. 1(d) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Comparative Example 8 (the fourth element M is Cr).
  • Fig. 1(e) shows a virtual cross section of a tomography tomographic image of the microstructure of the aluminum alloy material of Comparative Example 6 (where the fourth element M is Ni). Illustrations of other examples, comparative examples, and reference example 1 are omitted.
  • FIG. 2(a) shows a fracture surface of the aluminum alloy material (Std.: no fourth element M) of Comparative Example 1 after the tensile test.
  • FIG. 2(b) shows the fracture surface of the aluminum alloy material (the fourth element M is Zr) of Comparative Example 7 after the tensile test.
  • FIG. 2(c) shows a fracture surface of the aluminum alloy material (the fourth element M is Cr) of Comparative Example 8 after the tensile test.
  • FIG. 2(d) shows the fracture surface of the aluminum alloy material (the fourth element M is Sc) of Example 3 after the tensile test.
  • FIG. 2(e) shows the fracture surface of the aluminum alloy material of Example 4 (the fourth element M is Mn) after the tensile test.
  • FIG. 2( f ) shows the fracture surface of the aluminum alloy material (the fourth element M is Ti) of Example 1 after the tensile test.
  • FIG. 2(g) shows the fracture surface of the aluminum alloy material (the fourth element M is Ni) of Comparative Example 6 after the tensile test. Illustrations of other examples, comparative examples, and reference example 1 are omitted.
  • the hydrogen embrittlement inhibitors for aluminum alloy materials of Examples 1 to 5 can effectively prevent or suppress quasi-cleavage fracture of aluminum alloy materials, and are extremely effective as hydrogen embrittlement inhibitors for aluminum alloy materials. It turns out there is. Furthermore, from FIG. 3, according to a preferred embodiment of the present invention, the hydrogen embrittlement inhibitor for aluminum alloy materials of the present invention can effectively prevent or suppress intergranular fracture of aluminum alloy materials, and hydrogen embrittlement of aluminum alloy materials can be prevented. It was found that the fracture surface ratio (intergranular fracture and quasi-cleavage fracture) can be improved.
  • FIGS. 5(a) to 5(c) The crystal structure (first-principles calculation model) of particles formed by adding elements and their hydrogen trap sites are shown in FIGS. 5(a) to 5(c).
  • the crystal structure of the Al 3 Ti particles formed in Example 1 (where the fourth element M is Ti) and its hydrogen trap sites are shown in FIG. 5(b).
  • the crystal structure of Al 6 Mn particles formed in Example 4 (where the fourth element M is Mn) and its hydrogen trap sites are shown in FIG. 5(c). Illustrations of other examples, comparative examples, and reference example 1 are omitted. From FIGS.
  • the hydrogen trap energy is 0.785 eV/atom, 0.656 eV/atom and 0.883 eV/atom, all higher than 0.35 eV/atom for coherent precipitate interfaces and 0.55 eV/atom for semi-coherent precipitate interfaces. From the positive correlation between the hydrogen trap energy inside the particles and the quasi - cleavage fracture area ratio shown in FIG .
  • FIG. 6 shows the result of calculating the hydrogen trapping energy of each microstructure in the aluminum alloy material by first-principles calculation and the desired hydrogen trapping energy of the intermetallic compound particles (IMC particles).
  • IMC particles intermetallic compound particles
  • the hydrogen trap energy of the intermetallic compound particles (IMC particles) must be higher than at least 0.35 eV/atom of the coherent precipitate interface ( ⁇ 1 , coherent). Furthermore, in a preferred embodiment of the present invention, the hydrogen trapping energy of the intermetallic compound particles (IMC particles) is preferably higher than 0.55 eV/atom of the semi-coherent precipitate interface ( ⁇ 2 , semi-coherent). Separation of the ⁇ /Al interface due to hydrogen traps was calculated by first-principles calculations.
  • Table 3 shows the results of calculating the hydrogen trap energy inside the particles.
  • the hydrogen trap energy is 0.00% of the coherent precipitate interface ( ⁇ 1 , coherent). It was found to be higher than 35 eV/atom. Furthermore, when the hydrogen embrittlement inhibitor of the aluminum alloy material of Example 1, 3 or 5 of the preferred embodiment of the present invention is contained inside the material as a second phase particle, the hydrogen trap energy is semi-coherent precipitate interface ( ⁇ 2 , semi-coherent) is higher than 0.55 eV/atom.
  • FIG. 7 shows the relationship between the maximum hydrogen trap energy (E IMC ) inside the particle and the area fraction of quasi-cleavage fracture (A QCF ).
  • E IMC maximum hydrogen trap energy
  • a QCF area fraction of quasi-cleavage fracture
  • FIG. 7 shows the relationship between the maximum hydrogen trap energy (E IMC ) inside the particle and the area fraction of quasi-cleavage fracture (A QCF ).
  • QCF means quasi-cleavage creak. It can be read from FIG. 7 that there is a positive correlation between the hydrogen trap energy inside the particle and the quasi-cleavage fracture area ratio. It was found that hydrogen embrittlement can be prevented on the fractured surface after the tensile test. From the above, it was found that hydrogen embrittlement can be reduced by incorporating the hydrogen embrittlement inhibitor for the aluminum alloy materials of Examples 1 to 5 as second phase particles inside the materials.
  • the hydrogen embrittlement inhibitors for the aluminum alloy materials of Examples 1 to 4 were contained in the aluminum alloy material in micron order, at high density and dispersedly.
  • the hydrogen embrittlement inhibitors for aluminum alloy materials of Examples 1 to 5 can effectively prevent or suppress quasi-cleavage fracture of aluminum alloy materials, preferably prevent or suppress intergranular fracture, and prevent hydrogen embrittlement of aluminum alloy materials. It has been found to be very effective as an inhibitor.

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Abstract

Cet agent de prévention de fragilisation par l'hydrogène pour un matériau en alliage d'aluminium peut empêcher la fragilisation par l'hydrogène dans un matériau en alliage d'aluminium, et est destiné à une utilisation dans laquelle l'agent de prévention de la fragilisation par l'hydrogène est inclus en tant que secondes particules de phase à l'intérieur d'un matériau en alliage d'aluminium. Les secondes particules de phase comprennent au moins un type de particules parmi des particules de Sn, des particules de Al11Mn3Zn2, des particules de Al9Co2, des particules de Al6Mn, des particules de Al3Y, des particules de Al3Ti, des particules de Al3Sc, des particules de Al2Ca, des particules de Al7Cr, des particules de Al9Mn4, des particules de Al12Mn3Si et des particules de Al31Mn6Cu2. Cet agent de prévention de fragilisation par l'hydrogène pour un matériau en alliage d'aluminium peut empêcher ou supprimer efficacement la fragilisation par l'hydrogène.
PCT/JP2022/024630 2021-06-22 2022-06-21 Agent de prévention de fragilisation par l'hydrogène pour matériau en alliage d'aluminium WO2022270483A1 (fr)

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JPS62188762A (ja) * 1987-02-05 1987-08-18 Res Inst Electric Magnetic Alloys Ａｌ―Ｓｎ吸振合金およびその製造方法
JP2006336104A (ja) * 2005-05-31 2006-12-14 United Technol Corp <Utc> 高温アルミニウム合金
JP2009197249A (ja) * 2008-02-19 2009-09-03 Furukawa-Sky Aluminum Corp 高圧水素ガス用アルミニウム合金及び高圧水素ガス用アルミニウム合金クラッド材
JP2009221566A (ja) * 2008-03-18 2009-10-01 Kobe Steel Ltd 耐水素脆化特性に優れた高圧ガス容器用アルミニウム合金材
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