WO2011115202A1 - 高圧水素ガス貯蔵容器用アルミニウム合金材 - Google Patents
高圧水素ガス貯蔵容器用アルミニウム合金材 Download PDFInfo
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- WO2011115202A1 WO2011115202A1 PCT/JP2011/056369 JP2011056369W WO2011115202A1 WO 2011115202 A1 WO2011115202 A1 WO 2011115202A1 JP 2011056369 W JP2011056369 W JP 2011056369W WO 2011115202 A1 WO2011115202 A1 WO 2011115202A1
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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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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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
- C22F1/05—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 of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/14—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of aluminium; constructed of non-magnetic steel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0602—Wall structures; Special features thereof
- F17C2203/0604—Liners
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0636—Metals
- F17C2203/0646—Aluminium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0636—Metals
- F17C2203/0648—Alloys or compositions of metals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0107—Single phase
- F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/035—High pressure (>10 bar)
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/036—Very high pressure (>80 bar)
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2260/00—Purposes of gas storage and gas handling
- F17C2260/01—Improving mechanical properties or manufacturing
- F17C2260/011—Improving strength
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention relates to an AA6066 standard aluminum alloy material for a high-pressure hydrogen gas storage container.
- the main purpose of the present invention is a main body member of a high-pressure hydrogen gas storage container such as a liner, but the peripheral member of the high-pressure hydrogen gas storage container such as a base or a gas pipe is also used for a high-pressure hydrogen gas storage container. To express.
- the high-pressure hydrogen gas storage container using an aluminum alloy liner is not composed of an aluminum alloy alone, but a composite in which a fiber reinforced resin or reinforcing fiber is wound (filament winding) around the outer surface of the aluminum alloy liner.
- the mainstream is made of materials.
- Patent Document 1 discloses a method for manufacturing a high-pressure hydrogen gas storage container using an aluminum alloy liner from a high strength precipitation hardening type 7000 series aluminum alloy extruded material. That is, a 7000 series aluminum alloy extruded material is subjected to a drawing process, the drawn material is subjected to a solution treatment, and then an impact process is performed to form a bottomed cylindrical body. Thereafter, a gas outlet is formed by cold die forging and aging treatment is performed to manufacture a small high-pressure gas container.
- Patent Documents 2 and 3 propose that the proof stress of an aluminum alloy liner is further improved and the manufacturing method thereof is also improved. That is, it has been proposed that a solution treatment is applied to a 7000 series aluminum alloy material, and thereafter, ironing is performed to form a liner shape while imparting plastic strain, thereby omitting an aging treatment after the solution treatment.
- Patent Document 3 also discloses an aluminum alloy having a composition standardized to AA6066 (hereinafter also referred to as AA6066 standard aluminum alloy or AA6066 alloy) having excellent resistance to 7000 series and stress corrosion cracking resistance (SCC resistance). Proposed as a liner material.
- a liner material for such a 6066 aluminum alloy high-pressure hydrogen gas storage container is also proposed in Patent Document 4.
- This 6066 alloy is a precipitation hardening type aluminum alloy material having a high amount of Mg and Si and a relatively high strength among 6000 series aluminum alloys, and is expected to be a promising liner material for high-pressure hydrogen gas storage containers.
- the 7000 series aluminum alloy has higher strength than the 6066 alloy.
- 7000 series alloys have a large content of main elements such as Zn, Mg and Cu, and stress corrosion cracking (SCC) involving hydrogen embrittlement becomes a problem.
- SCC stress corrosion cracking
- the hydrogen embrittlement resistance is further deteriorated.
- the billet and slab are liable to crack during melt casting.
- cracks are likely to occur during hot working such as rolling, forging, and extrusion, and in extrusion, there is a problem that the extrusion speed becomes extremely low and productivity is lowered.
- this AA6066 alloy material is the most suitable material for a high-pressure hydrogen gas storage container among aluminum alloys.
- the improvement and combination of the above-described hydrogen embrittlement resistance and strength remain important improvements and improvement issues.
- Mg and Si contained in the AA6066 alloy composition are Mg ⁇ 1.73Si ⁇ 0.52%, Mg ⁇ 1.5%, Mg ⁇ 0.9%, and Si ⁇ 1.8. It has been proposed to improve the hydrogen embrittlement resistance of the AA6066 alloy by containing it within a specific range that satisfies the respective%.
- JP-A-6-63681 Japanese Patent No. 3750449 JP 2000-233245 A JP 2001-349494 A JP 2009-24225 A
- Patent Document 5 although the hydrogen embrittlement resistance can surely be improved, the mechanical properties of the AA6066 aluminum alloy material after the T6 tempering are based on the example, even if it has the highest strength, the tensile strength. Is 403 MPa, and the 0.2% proof stress is about 387 MPa. Therefore, it is necessary to increase the strength in order to reduce the thickness of the high-pressure hydrogen gas storage container in order to reduce the liner weight.
- the present invention has been made in view of such problems, and an object of the present invention is to provide an aluminum alloy material for a high-pressure hydrogen gas storage container that has higher strength while having excellent hydrogen embrittlement resistance.
- the gist of the present invention is, in mass%, Mg: 0.8 to 1.4%, Si: 0.9 to 1.8%, Fe: less than 0.44% (however, 0 %: Cu: 0.05-1.2%, Mn: 0.2-0.9%, Cr: 0.40% or less (including 0%), Zn: 0.25% or less (Including 0%), Ti: 0.20% or less (including 0%), respectively, the balance is made of Al and inevitable impurities, and the aluminum alloy structure has an equivalent circle diameter of 800 nm or less.
- the chemical component composition of the aluminum alloy material of the present invention is a standardized AA6066 alloy composition, and further limits the contents of Fe, Mn, and Cu to be narrower than the standard composition range, and Mg, The range of each content of Si, Cr, Zn, and Ti is the same as the standard range of AA6066.
- the said aluminum alloy material said by this invention includes the rolled sheet by hot rolling, the rolled sheet by cold rolling, the shape by hot extrusion, and the forging material by hot forging. Further, as mechanical properties after the T6 tempering of the aluminum alloy material, it is preferable that the tensile strength is 410 MPa or more, the 0.2% proof stress is 360 MPa or more, and the elongation is 10% or more.
- a fiber reinforced resin or a reinforcing fiber is wound around and suitably used as a high-pressure hydrogen gas storage container.
- the hydrogen embrittlement resistance of the aluminum alloy material is 5% of the case where the strain rate is 6.7 ⁇ 10 ⁇ 7 s ⁇ 1 or less and only the atmospheric conditions are changed and the aluminum alloy material is subjected to tensile deformation.
- the elongation value in a dry atmosphere below RH is ⁇ 1
- the elongation value in a highly humid atmosphere above 90% RH is ⁇ 2
- the hydrogen embrittlement susceptibility index represented by [( ⁇ 1- ⁇ 2) / ⁇ 1] is 0. It is preferably 1 or less (including negative values).
- the present inventors investigated the relationship between the composition, structure, hydrogen embrittlement resistance and strength of AA6066 alloy. As a result, it has been found that, among the compositions of the AA6066 alloy, the contents of Fe, Mn transition elements and Cu other than the main elements Mg and Si and particularly the hydrogen embrittlement resistance are greatly affected. Further, it has been found that the average density of dispersed particles formed by these transition elements and the average density of crystallized substances greatly influence the hydrogen embrittlement resistance.
- the content of the Fe transition element increases, the number (density) of dispersed particles and crystallized substances in the AA6066 alloy material structure increases. However, the behavior (action) of the dispersed particles and the crystallized materials are completely different from each other. If the (average) density of the dispersed particles increases, the hydrogen embrittlement resistance is greatly improved. It was found that the hydrogen embrittlement resistance greatly decreases as the (average) density of the object increases.
- the dispersed particles improve the hydrogen embrittlement resistance is that the dispersed particles have a function as a hydrogen trap (trapping) site in the 6066 alloy, and therefore, the effect of suppressing the accumulation of hydrogen at the crystal grain boundaries.
- the size of the dispersed particles is fine at the nano-order level when the material is produced by a conventional method. For this reason, even if hydrogen is trapped, it is unlikely to be the starting point of destruction, and it is assumed that the hydrogen embrittlement resistance is improved.
- the dispersed particles have the effect of suppressing recrystallization and making the crystal grains finer, and this is considered to lead to an improvement in hydrogen embrittlement resistance as well as an increase in strength. . Therefore, if a certain amount of these dispersed particles is secured, the hydrogen embrittlement resistance and strength are improved.
- the crystallized product is also considered to be a site where hydrogen accumulates.
- the interface between the crystallized material and the parent phase is a place where hydrogen easily enters the material.
- the crystallized substance is on the order of microns and is larger than the dispersed particles.
- the specific composition is further narrowed, and the aluminum alloy material has a structure in which a small amount of fine dispersed particles are dispersed and a coarse crystallized product is small.
- an aluminum alloy material having excellent hydrogen embrittlement resistance and high strength and suitable as a container for high-pressure hydrogen storage can be provided.
- the chemical composition of the aluminum alloy material of the present invention is that, as described above, the mechanical properties of the aluminum alloy material after T6 tempering are the mechanical properties necessary for a high-pressure hydrogen gas storage container.
- the specific composition is narrower than the composition range. That is, in order to control the dispersed particles and crystallized materials for the purpose of improving hydrogen embrittlement resistance and strength, among the main elements specified in the AA6066 alloy standard, in particular, the contents of Fe and Mn are specified. The balance is limited to a narrower range.
- the T6 tempering means that an aluminum alloy material is subjected to a peak aging treatment after a solution treatment and a quenching treatment.
- the chemical component composition of the aluminum alloy material of the present invention is narrower than the composition range of the standardized AA6066 alloy, and in mass%, Mg: 0.8 to 1.4%, Si: 0.9 ⁇ 1.8%, Fe: less than 0.44% (excluding 0%), Cu: 0.7-1.2%, Mn: 0.7-0.9%, Cr: 0.40%
- Mg 0.8 to 1.4%
- Si 0.9 ⁇ 1.8%
- Fe less than 0.44%
- Cu 0.7-1.2%
- Mn 0.7-0.9%
- Cr 0.40%
- Zn 0.25% or less
- Ti 0.20% or less (including 0%)
- the ranges of the contents of Mg, Si, Cu, Cr, Zn, and Ti to be defined are the same as the standard ranges (upper limit value and lower limit value) of AA6066. is there.
- % display of content of each element means the mass% altogether.
- the other elements other than these are impurities as in the standard of AA6066.
- the standard of AA6066 is 0.05% or less for individual elements, and the total amount (total) of these elements is 0.15% or less (allowable amount).
- the preferable content range and significance of each element, or the allowable amount will be described below for each element.
- Si 0.9-1.8% Si, together with Mg, partly dissolves in the aluminum alloy matrix and strengthens.
- the Si content is in the range of 0.9 to 1.8% in accordance with the standard of AA6066.
- Mg 0.8-1.4% Mg, like Si, strengthens the solid solution and forms aging precipitates that contribute to strength improvement together with Si during the artificial aging treatment, exerts age-hardening ability, and mechanical properties necessary as a high-pressure hydrogen gas storage container It is an essential element for obtaining the high strength and high proof stress necessary to satisfy the above. If the Mg content is too small, the absolute amount is insufficient, so that the solid solution strengthening and age hardening ability are insufficient. As a result, the required high strength and high yield strength cannot be obtained. On the other hand, when there is too much Mg content, intensity
- the Mg content is in the range of 0.8 to 1.4% in accordance with the standard of AA6066.
- Fe Less than 0.44% (excluding 0%), Fe is 0.50% or less (including 0%) as an impurity in the standard of AA6066.
- the Fe itself or the Fe content has been recognized only as an allowable amount as a general impurity inevitably contained from a melting raw material using scrap.
- Fe in order to allow a certain amount of fine dispersion particles of nano order to exist, Fe is contained as an essential element in a substantial amount of less than 0.44%. Fe, like Mn, forms a certain amount of average density that defines Al- (Fe, Mn, Cr) -based finely dispersed particles of the Al- (Fe, Mn, Cr) system during the homogenization heat treatment, and traps hydrogen. And improve the hydrogen embrittlement resistance. In addition, there is an effect of improving the strength by suppressing recrystallization and making the crystal finer.
- Fe is not contained in a substantial amount of less than 0.44%, too much or too little, the hydrogen embrittlement resistance is deteriorated.
- the average density D (particles / ⁇ m 2 ) of dispersed particles having an equivalent circle diameter of 800 nm or less and the average of crystallized substances having an equivalent circle diameter of 0.38 ⁇ m or more does not satisfy D ⁇ 0.0011 ⁇ C-6.6, and these effects are not exhibited.
- Fe is preferably 0 in order to ensure that these effects are reliably exhibited regardless of variations in the production conditions of the aluminum alloy material. 0.04% or more is contained.
- the Fe content is narrower than the standard of AA6066 and is limited to a range of less than 0.44% (but not including 0%).
- Mn 0.7 to 0.9%
- Mn forms a certain amount of average density that defines finely dispersed particles of the order of Al- (Fe, Mn, Cr) system during homogenization heat treatment, functions as a hydrogen trapping (trapping) site, Improve hydrogen embrittlement characteristics. Further, a part of Mn is dissolved in the aluminum alloy plate matrix to cause solid solution strengthening, and the dispersed particles have an effect of suppressing recrystallization and refining crystal grains.
- the Mn content is too small, and only a certain amount of average density that defines Al- (Fe, Mn, Cr) -based nano-order fine dispersed particles cannot be secured.
- the Mn content exceeds the upper limit of 0.9% defined in the present invention, coarse micron-order crystallized products are formed. On the contrary, the strength and hydrogen embrittlement resistance are lowered.
- the Mn content is narrower than the standard of AA6066 and is limited to a range of 0.7 to 0.9%.
- Cu 0.7 to 1.2% Cu contributes to the improvement of strength and proof stress together with Mg and Si. If the Cu content is too small, the effect cannot be sufficiently obtained, and the high strength and high proof stress necessary for satisfying the mechanical properties necessary for a high-pressure hydrogen gas storage container cannot be obtained. In addition, since the density of dispersed particles trapping hydrogen is lowered, the hydrogen embrittlement resistance is deteriorated. On the other hand, when there is too much Cu content, intensity
- Cr 0.40% or less (including 0%), Zn: 0.25% or less (including 0%), Ti: 0.20% or less (including 0%) Cr, Zn, and Ti are regulated as impurities.
- Cr forms dispersed particles in the same manner as Fe and Mn, but the amount added is smaller than that of Mn and Fe, and the effect of dispersed particles containing Cr is not as great as that of Fe and Mn.
- the content is too large, coarse micron-order crystallized products are formed, and on the contrary, the strength and hydrogen embrittlement resistance are lowered. Accordingly, Cr is regulated as an impurity to 0.40% or less (including 0%) as an AA6066 standard.
- Zn is regulated as an impurity to 0.25% or less (including 0%) as the standard of AA6066.
- Ti together with B contained in the mother alloy for Ti addition, has the effect of refining the crystal grains of the ingot, but if the Ti content is too high, it forms a coarse intermetallic compound, Reduces hydrogen embrittlement resistance.
- the formability of the plate and the workability such as rolling, extrusion, and forging during the production of the plate material and profile are greatly reduced. Therefore, Ti is restricted to 0.20% or less (including 0%) as impurities as AA6066 standard.
- the contents of Mg, Si, Cr, Zn, and Ti are the same as the standard range of AA6066 as described above.
- a certain amount of fine dispersed particles are present, and a structure in which coarse crystallized substances are regulated as few as possible. That is, in order to obtain hydrogen embrittlement resistance, the average density of dispersed particles having a circle-equivalent diameter of 800 nm or less is D (particles / ⁇ m 2 ) and the average density C of crystallized crystals having a circle-equivalent diameter of 0.38 ⁇ m or more ( 1 / mm 2 ) so that the expression D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 shown in FIG. In FIG.
- FIG. 1 is an arrangement of the average density D of dispersed particles and the average density C of crystallized materials in each example of Example Table 2 described later from the viewpoint of hydrogen embrittlement resistance, and the vertical axis represents the dispersion.
- the average density D of the particles and the horizontal axis are the average density C of the crystallized product.
- the average density C of the products is to be a value positioned in a region where the hydrogen embrittlement susceptibility index (elongation) on the left side of this straight line is 0.1 or less (including a negative value).
- the region on the right side of the straight line is a region where the hydrogen embrittlement susceptibility index (elongation) exceeds 0.1, and the average density D of dispersed particles or the average density C of crystallized material is located in this region. In this case, the hydrogen embrittlement resistance is inferior.
- the processing means such as a rolled plate, extruded material, or forged material can be used. Regardless, a certain amount of the finely dispersed particles described above can be present, and a coarse crystallized product can be regulated as little as possible. As a result, it does not become brittle even if the filling pressure of hydrogen gas in a high-pressure hydrogen gas storage container in an automobile-mounted application increases when it is used as a liner material regardless of a rolled plate, extruded material, or forged material. The hydrogen embrittlement resistance can be obtained. In addition, the strength can be increased to reduce the thickness to reduce the liner weight.
- the dispersed particles have a function as a hydrogen trapping site, and the size of the dispersed particles is fine at the nano-order level when a material is produced by a conventional method. For this reason, even if hydrogen is trapped, it does not become a starting point of destruction, and the strength and hydrogen embrittlement resistance are improved. Further, as is well known, the dispersed particles have an effect of refining crystal grains. Therefore, if a certain amount of these dispersed particles is secured as defined above, the hydrogen embrittlement resistance and strength are improved.
- the average density D (particles / ⁇ m 2 ) of dispersed particles having an equivalent circle diameter of 800 nm or less and the average density C (particles / mm 2 ) of crystallized particles having an equivalent circle diameter of 0.38 ⁇ m or more are dispersed.
- the average density D of the particles is larger than the value of ⁇ 0.0011 ⁇ C + 9.5, the number of fine dispersed particles (the number) of hydrogen trapping sites is excessive.
- the filling pressure of hydrogen gas in the high-pressure hydrogen gas storage container is increased, it is likely to become brittle.
- the dispersed particles defined in the present invention are mainly compounds of transition elements such as Mn and Al and Si, and may contain Fe. Further, depending on the amount of other transition elements such as Cr, Zr, V, etc., it is a compound containing these elements. These are mainly generated at the time of ingot casting, homogenization heat treatment of the ingot, and the like. However, since the maximum length level is greatly different (small) unlike the crystallized product, a TEM (transmission electron microscope) is generally used for the observation. However, only a narrow region can be observed, and there is a risk that the state of the microstructure in a specific region may be misunderstood as average information of the entire sample.
- TEM transmission electron microscope
- the dispersed particles defined in the present invention are observed and measured at a relatively high magnification of 10,000 times using an SEM (scanning electron microscope).
- the dispersed particles defined in the present invention need not be identified by elemental analysis (elemental amount analysis) using EDX or the like. That is, the second phase particles having a circle-equivalent diameter of 800 nm or less, which are observed (or can be observed) by the SEM under the above conditions, are all regarded as dispersed particles defined in the present invention.
- ultra-fine dispersed particles having a maximum equivalent circle diameter of less than 1 nm are difficult to accurately observe and measure the maximum length even with an SEM with a magnification of 10,000 times.
- the (capture) site effect is also considered small. Therefore, the lower limit of the preferable maximum length of the dispersed particles is 1 nm.
- the measurement surface of the average density of the dispersed particles defined in the present invention is the longitudinal direction (axis) of the pressure vessel member such as the aluminum alloy material after T6 tempering treatment and the liner formed and processed like the crystallized material.
- Crystallized product refers to a crystallized product crystallized at the time of casting, a micron-sized coarse Mg 2 Si formed at the time of homogenizing heat treatment or hot working and remaining even after the subsequent solution treatment. It is assumed that fine crystallized products and crystallized products also have a function as a hydrogen trapping (capturing) site, similar to the dispersed particles. However, when the material is produced by a conventional method, the existing crystallization product is on the order of microns and larger than the dispersed particles. For this reason, it is presumed that when hydrogen is trapped, it tends to be a starting point of destruction. Therefore, if these crystallized substances are restricted as much as possible, the hydrogen embrittlement resistance is improved, and the general toughness and fatigue characteristics are also improved.
- the average density C (particles / mm 2 ) of crystallized grains having an equivalent circle diameter of 0.38 ⁇ m or more is too large, the average density D (particles / ⁇ m 2 ) of dispersed particles having an equivalent circle diameter of 800 nm or less is large.
- D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 is not satisfied, and there are too many coarse crystallized substances that are the starting points of fracture, and the hydrogen embrittlement resistance is remarkably deteriorated.
- the crystallized substance specified in the present invention can be confirmed as an irregularly shaped particle existing in the matrix regardless of the composition by observation with an SEM having a magnification of about 300 times of the aluminum alloy material structure (the circle defined in the present invention). It can be determined whether the maximum equivalent diameter is 0.38 ⁇ m or less).
- These crystallized products are mainly Mg, Si-based compounds, Si, Fe-based compounds, etc. (however, in the case of containing many transition elements such as Cu and Mn, Cr, Zr, V, etc., These elements may be included). These include crystallized substances that crystallize during casting, coarse micron-sized Mg2MgSi, etc. that are formed during homogenization heat treatment and hot working and remain after the subsequent solution treatment.
- the composition of the second phase particles is not limited, elemental analysis (elements) of each crystallized substance using EDX (energy dispersive spectroscopy) or the like at the time of observation by the SEM (Quantitative analysis) is not necessary. That is, the coarse second-phase particles having an equivalent circle diameter of 0.38 ⁇ m or more observed with the SEM under the above conditions are all crystallized particles defined in the present invention.
- the maximum size of coarse crystallized particles cannot be predicted because it differs depending on the composition and manufacturing method, and all coarse crystallized particles having an equivalent circle diameter of 0.38 ⁇ m or more are subject to regulation. In the present invention, the upper limit of the maximum size of the crystallized particles is not defined.
- the measurement surface of the average density of the crystallized product specified in the present invention is the longitudinal direction (axis) of the pressure vessel member such as a liner obtained by molding and processing the aluminum alloy material after T6 tempering treatment, as with the dispersed particles.
- each crystallized substance observed as the second phase particles of any composition in the observation visual field is observed at a magnification of x300 and an acceleration voltage of 15 kV.
- image processing amorphous crystals are replaced with circles of the same area, the number of crystals having a maximum diameter of 0.38 ⁇ m or more is counted, and the number per unit area 1 mm 2 of the measurement field, that is, density (pieces) / mm 2 ) is calculated.
- all crystallized substances observed by SEM are evaluated. The measurement is performed at any five points in the cross section of each test wire rod, and each of the two visual fields (total 10 visual fields) is averaged to obtain the average density of the crystallized product defined in the present invention.
- the alloy composition of the specific composition is 6066, as long as the temperature of the homogenization heat treatment is taken care of, a rolled plate by hot rolling, a rolled plate by cold rolling, a profile by hot extrusion, or a forging material by hot forging
- the aluminum alloy material of the present invention can be produced by a conventional method. That is, the aluminum alloy material structure of the present invention in which a certain amount of fine dispersed particles are present and the amount of coarse crystallized substances is regulated as little as possible can be obtained.
- the 6066 alloy ingot of the specific composition is melted and the ingot is subjected to homogenization heat treatment, followed by hot rolling and further cold rolling as necessary to obtain a cold rolled plate having a desired thickness, Alternatively, hot extrusion or hot forging is performed to obtain a 6066 alloy profile or forging having a desired thickness and shape.
- hot extrusion or hot forging is performed to obtain a 6066 alloy profile or forging having a desired thickness and shape.
- the molten aluminum alloy melt-adjusted within the specific 6066 composition range is cast by appropriately selecting a normal melting casting method such as a semi-continuous casting method (DC casting method).
- the cast aluminum alloy ingot Prior to the above-mentioned various hot workings, the cast aluminum alloy ingot is subjected to a homogenization heat treatment (soaking) in a relatively high temperature range of 540 ° C. or more to homogenize the structure (within the crystal grains in the ingot structure).
- the crystallized product is refined.
- the soaking temperature is relatively low, 350 to 550 ° C. (540 ° C. in the embodiment)
- the crystallization product can be refined even within the composition of the present invention.
- the soaking temperature is too high, the dispersed particles are coarsened and the density tends to be low. There is a risk that the number of hydrogen trap sites is reduced and the hydrogen embrittlement resistance is deteriorated. Further, since the dispersed particles are coarse and low in density, recrystallization is likely to occur, and the crystal grains are also coarsened, so that the strength is low and easy. Also, ingot burning is likely to occur. Therefore, the upper limit of the soaking temperature is 575 ° C.
- the billet (ingot) After this soaking process, it is preferable to forcibly quench the billet (ingot) with a fan or the like to increase the cooling rate. If the cooling rate is slow, such as allowing the billet (ingot) to cool, there is a risk of the crystallized material becoming coarse during the cooling process.
- the standard of the average cooling rate in such rapid cooling is preferably 80 ° C./hr or higher up to a temperature of 300 ° C. or lower including room temperature.
- Hot working such as hot rolling, hot extrusion, hot forging, etc. is performed by a conventional method.
- the hot working start temperature is selected from the range of 350 to 575 ° C. in relation to the composition of the aluminum alloy and the size of the ingot.
- the processing rate of hot working is also selected from a range of processing rates of 85% or more depending on the composition of the aluminum alloy and the relationship between the ingot size and the desired thickness of the aluminum alloy material (product). If the processing rate is too small, the crystallized product is not pulverized to a small size, and coarse crystallized product remains, and the crystallized product cannot be refined as defined in the present invention.
- the ingot after the homogenization heat treatment is cooled to the hot rolling temperature, or once cooled to room temperature and then reheated to the hot rolling temperature, hot rolled, and hot rolled to a desired thickness.
- a rolled sheet is obtained or further cold-rolled as necessary to obtain a cold-rolled sheet having a desired thickness and then tempered.
- the ingot after the homogenization heat treatment is reheated, hot extruded to a desired thickness and shape in the range of 350 to 575 ° C, and further cold-extruded to the desired shape and thickness as required ( Draw core) and then temper.
- a forged material is the ingot after the homogenization heat treatment reheated and hot forged to a desired thickness and shape within a range of 350 to 575 ° C. to obtain a hot forged material having a desired thickness?
- hot forging, warm forging, and cold forging are performed to obtain a forged material having a desired thickness, and then tempering.
- tempering treatment After these hot workings, as a tempering treatment for the aluminum alloy material, first, solution treatment and rapid cooling (quenching) treatment are performed. This solution treatment is preferably performed at a temperature of 530 ° C. or higher in order to sufficiently precipitate aging precipitates that contribute to strength improvement by the relationship with the component composition of the aluminum alloy and the subsequent artificial age hardening treatment at a high temperature. 570 is performed under the condition of holding for a predetermined time. Immediately after the solution treatment, rapid cooling (quenching) is performed at a cooling rate of 10 ° C./second or more. When the cooling rate of the rapid cooling treatment after the solution treatment is slow, Si, MgSi compounds and the like are likely to precipitate on the grain boundaries, and mechanical properties and formability are deteriorated.
- any of a batch furnace, a continuous furnace, and a molten salt bath furnace may be used as a heat treatment furnace used for solution treatment and quenching treatment.
- the quenching treatment after the solution treatment may be any of water immersion, water jetting, mist jetting, air jetting, and air cooling.
- any of a batch furnace, a continuous furnace, an oil bath, a hot water bath, etc. may be used for the high temperature aging treatment performed after the solution treatment and the quenching treatment.
- a high temperature aging treatment at 150 to 200 ° C. is preferably performed immediately in order to improve mechanical properties such as strength.
- This tempering is a tempering symbol T6 (solution treatment and quenching treatment + peak aging treatment) performed under the heat treatment conditions described in JISH-0001, for example.
- T6 solution treatment and quenching treatment + peak aging treatment
- the mechanical properties after the T6 tempering of the aluminum alloy material are a tensile strength of 410 MPa or more, a 0.2% proof stress of 360 MPa or more, and an elongation of 10% or more. It becomes difficult to obtain mechanical properties.
- the cast billet is reheated and hot extruded so that the temperature of the extruded material on the outlet side of the hot extrusion is in the solution temperature range, and then the extruded material is immediately after the extrusion.
- Forcibly cooling and quenching may be performed online by water injection, mist injection, air injection, or the like to a temperature near room temperature.
- high temperature aging treatment may be performed after room temperature aging and distortion correction as necessary.
- high temperature An aging treatment T6 may be performed.
- the above-described tempering may be selected and performed on the plate material, the extruded material, and the forged material in advance before preparing the member for the high-pressure gas container.
- the T6 tempering treatment is performed according to the required characteristics of each member after producing these high-pressure gas container materials and peripheral members. Each may be selected.
- the tempering treatment and the quenching treatment may be performed separately, such as performing the high pressure gas container material and the peripheral member before the production, and performing the peak aging treatment after the production.
- This cold-rolled sheet was quenched by water quenching (described as WQ in Table 2) immediately after solution treatment at 550 ° C. ⁇ 3 hours (hr) shown in Table 2 in a batch furnace. It was. Then, after 3 days of room temperature aging (15-35 ° C), after correcting the distortion of the plate with a leveler, 180 ° C ⁇ 9 hours of peak aging treatment, T6 (after solution treatment and quenching) Each tempered material of peak aging treatment was prepared. An air furnace was used for soaking, heating to hot rolling temperature, and high temperature aging treatment. The cooling rate in the case of water quenching immediately after the solution treatment shown in Table 2 is about 250 ° C./second. Incidentally, the cooling rate in the case of forced air cooling by a fan is about 50 ° C./min.
- sample material properties The external dimensions of the tempered plate materials thus manufactured were 1.0 mm in length and 200 mm in width in common with each example. Then, from the plate material after room temperature aging (elapsed) for 30 days after the high temperature aging treatment of this plate, a test material (plate-shaped test piece) was cut out, and the microstructure, tensile properties, hydrogen embrittlement resistance of each test material were cut out. The crystallization characteristics were measured and evaluated. These results are shown in Table 2.
- Microstructure The average density (particles / ⁇ m 2 ) of directly dispersed particles having an equivalent circle diameter of 800 nm or less and the average density of crystallized substances having an equivalent circle diameter of 0.38 ⁇ m or more (pieces / mm 2 ) of each test material are: Each was measured by the method described above.
- Tensile test In the tensile test, a JIS No. 5 test piece (GL 50 mm) of JISZ2201 was sampled from the test material so that the longitudinal direction of the test piece was perpendicular to the rolling direction, and pulled at room temperature in air at a crosshead speed of 5 mm / min. A test was conducted. The measured N number was 5, and each mechanical property was an average of these values.
- the hydrogen embrittlement resistance of the test material is 5% RH or less when the aluminum alloy material is subjected to tensile deformation only by changing the atmospheric condition with a strain rate of 6.7 ⁇ 10 ⁇ 7 s ⁇ 1 or less.
- the elongation value in a dry atmosphere is ⁇ 1
- the elongation value in a high-humidity atmosphere of 90% RH or higher is ⁇ 2.
- a small tensile test piece having a width of 5 mm, a length of 12 mm, and a shoulder radius of 7.5 mm from the test material is set so that the longitudinal direction of the test piece is perpendicular to the rolling direction of the plate.
- the sample was sampled and pulled to break at two initial strain rates of 6.7 ⁇ 10 ⁇ 7 s ⁇ 1 , and in two conditions: a dry atmosphere of 5% RH or less and a highly humid atmosphere of 90% RH or more.
- a test was conducted. Then, the rate of decrease of the elongation value ⁇ 2 in the highly humid atmosphere of 90% RH or more relative to the elongation value ⁇ 1 in the dry atmosphere of 5% RH or less was calculated by the above formula. It can be evaluated that the hydrogen embrittlement resistance is excellent as the decrease rate of these elongation values is 0.1 or less, more preferably 0.05 or less.
- the rate of decrease in elongation value of 0.05 means that a 6061-T6 material that has been proven to be excellent in hydrogen embrittlement resistance in a hydrogen container member was tested for hydrogen embrittlement resistance under the same conditions as described above. This is the reference value obtained. Further, the elongation reduction rate of 10% was obtained by testing the hydrogen embrittlement resistance test under the same conditions as described above for 7050-T7 material which is not a hydrogen container member but has a proven track record as a structural member having excellent corrosion resistance. This is the reference value.
- Invention Examples 1 to 3 have both high strength and hydrogen embrittlement resistance. That is, each of the inventive examples satisfies the aluminum alloy composition of the present invention, and the production conditions including tempering are appropriate. For this reason, the relationship between the average density of dispersed particles having a circle-equivalent diameter of 800 nm or less and D (particles / ⁇ m 2 ) and the average density C (particles / mm 2 ) of crystallized particles having a circle-equivalent diameter of 0.38 ⁇ m or more is , D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 (D ⁇ ⁇ 0.0011 ⁇ C + 9.5), a fine dispersed particle is dispersed in a certain amount, and there is little coarse crystallized structure.
- the tensile strength is 410 MPa or more
- the 0.2% proof stress is 360 MPa or more
- the elongation is 10% or more
- the hydrogen embrittlement susceptibility index is 0.1 or less even under high-pressure hydrogen gas. Combines hydrogen embrittlement resistance.
- Comparative Examples 1 to 3 do not satisfy both strength and hydrogen embrittlement resistance. That is, each comparative example does not satisfy the aluminum alloy composition of the present invention or the manufacturing method is inappropriate.
- Comparative Example 1 Although the Fe content is within the standard range of AA6066, it exceeds the upper limit of the present invention and is too much. For this reason, although the production conditions are appropriate and a certain amount of fine dispersed particles are dispersed, there are too many coarse crystallized products, and D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 (D ⁇ ⁇ 0.0011 ⁇ C + 9.5) is not satisfied and the hydrogen embrittlement resistance is inferior to that of the inventive examples.
- Comparative Example 2 has too little Cu content, and is outside the standard range of the present invention and AA6066. For this reason, the manufacturing conditions are appropriate, the formula of D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 is satisfied, and the hydrogen embrittlement resistance is high, but the strength is inferior to that of the inventive examples.
- Comparative Example 3 has too little content of Mn and is outside the standard range of the present invention and AA6066. For this reason, the manufacturing conditions are appropriate, the formula D + 0.0011 ⁇ C ⁇ 9.5 ⁇ 0 is satisfied, and the hydrogen embrittlement resistance is high, but the strength is lower than that of the inventive examples.
- a 6000 series aluminum alloy material for a high-pressure hydrogen gas storage container having excellent strength and hydrogen embrittlement resistance. Therefore, a 6000 series aluminum alloy material can be applied as a member such as a liner, a cap, or a gas pipe to a high-pressure gas container in which reinforcing fibers are wound around the outer surface of an aluminum alloy or plastic liner.
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Abstract
Description
先ず、本発明材のアルミニウム合金の化学成分組成について、各元素の限定理由を含めて、以下に説明する。本発明アルミニウム合金材の化学成分組成は、アルミニウム合金材のT6調質後の機械的な性質を、高圧水素ガス貯蔵容器として必要な機械的な性質とするために、前記した通り、AA6066合金の組成範囲よりも更に狭い特定組成とする。すなわち、耐水素脆化特性や強度の向上を目的として、分散粒子や晶出物を制御するために、AA6066合金規格に規定された主要元素の中でも、特に、Fe、Mnの含有量を、規格よりも狭い範囲に限定して、よりバランスさせる。なお、前記T6調質とは、アルミニウム合金材を溶体化処理および焼入れ処理後にピーク時効処理を施すことである。
Siは、Mgとともに、一部がアルミニウム合金マトリックスに固溶し、固溶強化する。また、前記比較的高温での人工時効処理時に強度向上に寄与する時効析出物などを形成する時効硬化能を発揮して、高圧水素ガス貯蔵容器として必要な機械的性質を満たすのに必要な、前記高強度、高耐力を得るための必須の元素である。Si含有量が少なすぎると、絶対量が不足するため、前記固溶強化や時効硬化能が不足する。この結果、必要な前記高強度、高耐力を得ることができない。一方で、Siの含有量が多過ぎると、強度が高くなり過ぎ、耐食性や耐水素脆化特性が低下する。また、マトリックスに固溶できないため、粗大な晶出物および析出物を形成し、耐水素脆化特性が低下するとともに、強度、伸びなどの低下の原因となり、また板材や形材製造時の圧延や押出、鍛造などの加工性も低下する。したがって、Siの含有量は、AA6066の規格通り、0.9~1.8%の範囲とする。
Mgは、Siと同様、固溶強化と、前記人工時効処理時にSiとともに強度向上に寄与する時効析出物を形成して、時効硬化能を発揮し、高圧水素ガス貯蔵容器として必要な機械的特性を満たすのに必要な、前記高強度、高耐力を得るための必須の元素である。Mg含有量が少なすぎると、絶対量が不足するため、前記固溶強化や時効硬化能が不足する。この結果、必要な前記高強度、高耐力を得ることができない。一方、Mg含有量が多すぎると、強度が高くなり過ぎ、耐食性や耐水素脆化特性が低下する。また、マトリックスに固溶できないため、粗大な晶出物および析出物を形成し、耐水素脆化特性が低下するとともに、強度、伸びなどの低下の原因となり、また板材や形材製造時の圧延や押出、鍛造などの加工性も低下する。したがって、Mgの含有量は、AA6066の規格通り、0.8~1.4%の範囲とする。
Feは、AA6066の規格では、不純物として0.50%以下(但し0%を含む) である。ただ、前記特許文献5などでは、これを超えて、0.65%まで含有させている実施例もある。したがって、これまでFe自体あるいはFeの含有量については、スクラップを使用した溶解原料などから必然的に含まれる一般的な不純物としての許容量としてしか、認識されてこなかった。
Mnは、均質化熱処理時にAl-(Fe,Mn,Cr)系のナノオーダーの微細な分散粒子を規定する一定量の平均密度だけ形成して、水素のトラップ(捕捉)サイトとして機能し、耐水素脆化特性とを向上させる。また、Mnの一部がアルミニウム合金板マトリックスに固溶し固溶強化を生じ,また、分散粒子は再結晶の抑制ならびに結晶粒を微細化させる効果もある。
Cuは、Mg、Siと共に強度、耐力の向上に寄与する。Cu含有量が少なすぎると、その効果が十分に得られず、高圧水素ガス貯蔵容器として必要な機械的特性を満たすのに必要な、前記高強度、高耐力を得ることができない。また、水素をトラップする分散粒子の密度は低くなるため、耐水素脆化特性を劣化する。一方、Cu含有量が多すぎると、却って、強度、耐力が低下する。また、板の成形性や板材や形材製造時の圧延や押出、鍛造などの加工性そして耐食性が大きく低下する。晶出物の密度は高くなり、耐水素脆化特性は劣化する。したがって、Cuの含有量は、AA6066の規格通り、0.7~1.2%の範囲とする。
Cr、Zn、Tiは各々不純物として規制する。このうち、Crは、Fe、Mnと同様に、分散粒子を形成するものの、添加量はMn、Feに比べ少なく、Crを含む分散粒子の効果は、Fe、Mnほどには大きくない。また、含有量が多すぎると、粗大なミクロンオーダーの晶出物が生成して、却って、強度と耐水素脆化特性とを低下させる。したがって、Crは不純物として、AA6066の規格通り、0.40%以下(但し0%を含む)に規制する。
本発明では、Mg、Si、Cr、Zn、Tiの含有量は、前記した通り、AA6066の規格範囲と同じである。その上で、微細な分散粒子を一定量存在させるとともに、粗大な晶出物をできるだけ少なく規制した組織とする。すなわち、耐水素脆化特性を得るために、800nm以下の円相当径の分散粒子の平均密度をD(個/μm2)と0.38μm以上の円相当径の晶出物の平均密度C(個/mm2)との関係が、図1に示すD+0.0011×C-9.5≦0の式を満たすようにする。なお、図1では、このD+0.0011×C-9.5≦0の式を変形したD≦-0.0011×C+9.5の式で示している。この図1は、後述する実施例表2の各例の分散粒子の平均密度Dと晶出物の平均密度Cとを耐水素脆化特性の観点から整理したものであり、縦軸が前記分散粒子の平均密度D、横軸が晶出物の平均密度Cである。そして、横軸の晶出物の平均密度8200個/mm2近傍から左上に向かって斜めに立ち上がる直線がD=-0.0011×C+9.5の式である。ここで、本発明が規定するD+0.0011×C-9.5≦0、すなわちD≦-0.0011×C+9.5の式を満たすとは、図1において、分散粒子の平均密度Dおよび晶出物の平均密度Cをともに、この直線よりも左側の水素脆化感受性指標(伸び)が0.1以下(マイナスの値も含む)となる領域に位置させる値にすることである。言い換えると、この直線よりも右側の領域は水素脆化感受性指標(伸び)が0.1を超える領域であり、分散粒子の平均密度Dか晶出物の平均密度Cをこの領域に位置させた場合には、耐水素脆化特性が劣ることとなる。
分散粒子は、水素のトラップ(捕捉)サイトとしての機能があり、かつこの分散粒子の大きさは、常法により材を製造した場合、ナノオーダーレベルで微細である。このため、水素をトラップしても、破壊の起点とはなりにくく、強度と耐水素脆化特性とを向上させる。また、分散粒子には、周知の通り、結晶粒を微細化せる効果がある。したがって、これらの分散粒子を、上記規定の通り一定量確保すれば、耐水素脆化特性と強度とが向上する。
本発明で規定する分散粒子の平均密度の測定面は、晶出物と同様、T6調質処理後のアルミニウム合金材や、これを成形、加工したライナーなどの圧力容器部材の、長手方向(軸方向)に対する平行な任意の断面の中央部とする。これら平行断面中央部より、試料を作製し、成分分析装置付属のSEM(走査型電子顕微鏡)を用いて、倍率×10000、加速電圧15kVで観察する。画像処理で、不定形の分散粒子を同一面積の円に置き換え、その円相当径(直径)の最大径が800nm以下の分散粒子の数をカウイントし、観察面積当たりの個数すなわち密度(個/μm2)を算出する。一般的に、加速電圧15kVの場合、母材がAlであれば、電子線の侵入深さは2ミクロン強で、観察される深さはその1/3程度とされる。試料表面の分散粒子のみを評価対象とするため、画像処理する際は、試料内部に存在する粒子に対応するぼやけた像は、画像上から削除することとする。なお、試料表面の分散粒子は、明瞭な輝点(白黒の画像であれば、白色の点)として観察される。測定は、各供試線棒材の任意の前記断面5箇所で、各2視野(計10視野)について行い、これらを平均化し、本発明で規定する分散粒子の平均密度とする。
晶出物とは、鋳造時に晶出する晶出物や、均質化熱処理時、熱間加工時に形成されその後の溶体化処理時後でも残存するミクロンサイズの粗大なMg2 Si等を指す。微細な晶出物や晶出物にも、前記分散粒子と同様に、水素のトラップ(捕捉)サイトとしての機能はあると推考される。しかし、常法により材を製造した場合、存在する晶出物は大きさがミクロンオーダーと、分散粒子よりも巨大である。このため、水素をトラップした場合に、破壊の起点となり易くなるものと推定される。したがって、これらの晶出物をできるだけ少なく規制すれば、耐水素脆化特性が向上するとともに、さらには一般的な靱性、疲労特性も高くなる。
本発明で規定する晶出物の平均密度の測定面は、分散粒子と同様、T6調質処理後のアルミニウム合金材や、これを成形、加工したライナーなどの圧力容器部材の、長手方向(軸方向)に対する平行な任意の断面の中央部とする。これら平行断面中央部の位置における組織の走査型電子顕微鏡(SEM)による倍率300倍、加速電圧15kVの観察から、計測、算出される。
前記特定組成の6066合金組成とすれば、均質化熱処理の温度さえ注意すれば、熱間圧延による圧延板や、冷間圧延による圧延板、あるいは熱間押出による形材や熱間鍛造による鍛造材など、常法によって、本発明アルミニウム合金材を製造できる。すなわち、上記した、微細な分散粒子を一定量存在させるとともに、粗大な晶出物をできるだけ少なく規制した本発明アルミニウム合金材組織とすることができる。
先ず、溶解、鋳造工程では、上記特定の6066組成範囲内に溶解調整されたアルミニウム合金溶湯を、半連続鋳造法(DC鋳造法)等の通常の溶解鋳造法を適宜選択して鋳造する。
前記した種々の熱間加工に先立って、鋳造されたアルミニウム合金鋳塊を540℃以上の比較的高温域で均質化熱処理(均熱処理)し、組織の均質化(鋳塊組織中の結晶粒内の偏析をなくすなど)とともに、晶出物を微細化する。前記特許文献5のように、この均熱処理温度を350~550℃(その実施例では540℃)と比較的低温した場合には、本発明組成内であっても、晶出物を微細化出来ずに、粗大な晶出物が多くなる危険性がある。したがって、破壊の起点となる晶出物が多過ぎ、耐水素脆化特性の低下さらには靱性、疲労特性の低下をもたらす危険性が高くなる。
一方、均熱処理温度が高くなり過ぎると、分散粒子は粗大化し密度は低くなり易くなる。水素のトラップサイトは減り、耐水素脆化特性を低下させる危険性がある。また、分散粒子の粗大、低密度化で、再結晶が生じ易くなり、また結晶粒も粗大化するため、強度は低くやり易い。また、鋳塊のバーニングも生じ易くなる。従って、均熱処理温度の上限は575℃とする。
熱間圧延、熱間押出、熱間鍛造などの熱間加工は常法による。言い換えると、特別な条件は不要で、熱間加工開始温度は、前記アルミニウム合金の成分組成や鋳塊の大きさとの関係で、350~575℃の範囲から選択する。熱間加工の加工率も、前記アルミニウム合金の成分組成や、鋳塊の大きさとアルミニウム合金材(製品)の所望厚みとの関係で、85%以上の加工率の範囲から選択する。この加工率が少なすぎると、晶出物が小さく粉砕されず、粗大な晶出物が残存して、本発明で規定するようには晶出物を微細化できない。
また、鍛造材の場合、均質化熱処理後の鋳塊を再加熱し、350~575℃の範囲で所望の厚みと形状に熱間鍛造して、所望の肉厚の熱間鍛造材を得るか、更に必要に応じて熱間鍛造、温間鍛造、冷間鍛造して、所望の肉厚の鍛造材とし、その後調質する。なお、熱間鍛造、温間鍛造、冷間鍛造の間のパス間に、必要に応じて焼鈍を行ってもよい。
これらの熱間加工後に、アルミニウム合金材に対する調質処理として、先ず、溶体化および急冷(焼入れ)処理を行う。この溶体化処理は、前記アルミニウム合金の成分組成との関係や、続く高温での人工時効硬化処理により強度向上に寄与する時効析出物を十分粒内に析出させるために、好ましくは、530℃~570で所定時間保持する条件で行う。この溶体化処理後、直ちに10℃/秒以上の冷却速度で急冷処理(焼入れ処理)を行う。この溶体化処理後の急冷処理の冷却速度が遅いと、粒界上にSi、MgSi化合物などが析出しやすくなり、機械的な特性や成形性を低下させる。
これら製作した調質後の板材の外寸形状は、各例とも共通して、長さ1.0mm、幅200mmとした。そして、この板の高温時効処理後から30日間の室温時効(経過)後の板材から、供試材(板状試験片)を切り出し、これら各供試材のミクロ組織、引張特性、耐水素脆化特性を測定、評価した。これらの結果を表2に示す。
各供試材の800nm以下の円相当径の直分散粒子の平均密度(個/μm2 )と、0.38μm以上の円相当径の晶出物の平均密度が(個/mm2 )は、各々前記した方法で測定した。
引張試験は、前記供試材からJISZ2201のJIS5号試験片(GL50mm)を圧延方向に対して試験片長手方向が直角となるように採取し、室温大気中で、クロスヘッド速度5mm/分で引張試験を行った。測定N数は5として、各機械的性質はこれらの平均値とした。
前記供試材の耐水素脆化特性は、歪み速度を6.7×10-7 s-1 以下として雰囲気条件のみを変えて、このアルミニウム合金材を引張変形させた場合の5%RH以下の乾燥雰囲気中での伸び値をδ1、90%RH以上の高湿潤雰囲気中での伸び値をδ2として、[(δ1-δ2)/δ1]で示されるものを、耐水素脆化感受性指標とした。具体的には、前記供試材から幅5mm、長さ12mmの平行部、肩部半径7.5mmの小型引張試験片を、板の圧延方向に対して試験片長手方向が直角となるように採取し、初期歪速度6.7×10-7 s-1 で、雰囲気条件を5%RH以下の乾燥雰囲気中、90%RH以上の高湿潤雰囲気中との2つの条件で、各々破断まで引張試験を行った。そして、5%RH以下の乾燥雰囲気中の伸び値δ1に対する、90%RH以上の高湿潤雰囲気中の伸び値δ2の低下率を上記式にて算出した。これら伸び値の低下率が0.1以下、より好ましくは0.05以下と小さいほど、耐水素脆化特性が優れていると評価出来る。
Claims (3)
- 質量%で、Mg:0.8~1.4%、Si:0.9~1.8%、Fe:0.44%未満(但し0%は含まず) 、Cu:0.7~1.2%、Mn:0.7~0.9%、Cr:0.40%以下(但し0%を含む) 、Zn:0.25%以下(但し0%を含む) 、Ti:0.20%以下(但し0%を含む) を各々含み、残部がAlおよび不可避的不純物よりなり、このアルミニウム合金組織における、800nm以下の円相当径を有する分散粒子の平均密度をD(個/μm2)、0.38μm以上の円相当径を有する晶出物の平均密度C(個/mm2)とした時、これらCとDとの関係が、D+0.0011×C-9.5≦0の式を満たすことを特徴とする高圧水素ガス貯蔵容器用アルミニウム合金材。
- 前記アルミニウム合金材のT6調質後の機械的な性質として、引張強さが410MPa以上、0.2%耐力が360MPa以上、伸びが10%以上であり、ライナー材として外側に繊維強化樹脂あるいは強化用繊維が巻き付けられて高圧水素ガス貯蔵容器として使用されるものである請求項1に記載の高圧水素ガス貯蔵容器用アルミニウム合金材。
- 前記アルミニウム合金材の耐水素脆化感受性が、歪速度を6.7×10-7 s-1 として雰囲気条件のみを変えて、このアルミニウム合金材を引張変形させた場合の5%RH以下の乾燥雰囲気中での伸び値をδ1、90%RH以上の高湿潤雰囲気中での伸び値をδ2として、[(δ1-δ2)/δ1]で示される水素脆化感受性指標が0.1以下(マイナスの値も含む)である請求項1または2に記載の高圧水素ガス貯蔵容器用アルミニウム合金材。
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EP3584492A4 (en) * | 2017-02-15 | 2021-03-17 | Bogachek, Oleg Evgenievich | THERMALLY NON-HARDENING ALUMINUM ALLOY CONTAINER AND PRODUCTION PROCESS |
US11644151B2 (en) | 2017-02-15 | 2023-05-09 | Oleg Evgenievich BOGACHEK | Vessel made of thermally non-hardenable aluminum alloy and method for the production thereof |
Also Published As
Publication number | Publication date |
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EP2548984A1 (en) | 2013-01-23 |
CN102812141A (zh) | 2012-12-05 |
US20130164170A1 (en) | 2013-06-27 |
EP2548984B1 (en) | 2016-07-20 |
KR20120123711A (ko) | 2012-11-09 |
EP2548984A4 (en) | 2015-06-24 |
JP5610582B2 (ja) | 2014-10-22 |
US9249483B2 (en) | 2016-02-02 |
CN102812141B (zh) | 2014-08-06 |
KR101457774B1 (ko) | 2014-11-03 |
JP2011214149A (ja) | 2011-10-27 |
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