WO2025180366A1 - 一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆 - Google Patents

一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆

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Publication number
WO2025180366A1
WO2025180366A1 PCT/CN2025/079063 CN2025079063W WO2025180366A1 WO 2025180366 A1 WO2025180366 A1 WO 2025180366A1 CN 2025079063 W CN2025079063 W CN 2025079063W WO 2025180366 A1 WO2025180366 A1 WO 2025180366A1
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WO
WIPO (PCT)
Prior art keywords
aluminum alloy
cylinder liner
hydrogen storage
alloy plate
storage cylinder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2025/079063
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English (en)
French (fr)
Inventor
武昌
刘俊涛
杨兵
曾渝
陈纪强
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Baoshan Iron and Steel Co Ltd
Original Assignee
Baoshan Iron and Steel Co Ltd
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Filing date
Publication date
Application filed by Baoshan Iron and Steel Co Ltd filed Critical Baoshan Iron and Steel Co Ltd
Publication of WO2025180366A1 publication Critical patent/WO2025180366A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • 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
    • 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
    • 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
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials

Definitions

  • the present invention relates to the technical field of metal materials and processing thereof, and in particular to an aluminum alloy plate for a high-strength and high-pressure hydrogen storage cylinder liner, a preparation method and the cylinder liner.
  • the metal liner material is usually aluminum alloy, but the high-strength and toughness aluminum alloys with grades such as 2xxx and 7xxx have weak spinning forming capabilities. There is an urgent need for an aluminum alloy material with strong forming capabilities and high strength and toughness to make the metal liner of the hydrogen storage container.
  • Chinese patent CN 112743878 A discloses "Fiber composite material high-pressure hydrogen storage cylinder and its preparation method", which wraps T700 carbon fiber around the outer surface of a 6061 aluminum liner to enhance the strength and durability of the hydrogen cylinder, and improve the performance and safety of the hydrogen cylinder for high-pressure hydrogen storage.
  • its final burst pressure value can reach more than 170MPa, and its fatigue loading life can reach more than 10,000 times, which is consistent with the technical performance of the current mainstream Type III cylinders.
  • a high-pressure hydrogen storage cylinder with light weight, high strength, fatigue resistance, high structural rigidity, and good high and low temperature impact stability is obtained.
  • the patent does not mention the relevant technology of the aluminum material required for the aluminum liner.
  • Chinese patent CN 115382984 A discloses "a stamping method and drawing die for large-volume aluminum alloy liners of hydrogen storage cylinders".
  • the aluminum alloy liners of hydrogen storage cylinders can be produced by hot stamping of aluminum ingots, then turning, and finally cold drawing.
  • This method does not require strong spinning and thinning, and effectively solves the technical problem of low production efficiency of large-volume aluminum alloy liners of hydrogen storage cylinders produced by strong spinning and thinning of aluminum tubes.
  • the patent does not mention the relevant technology of the aluminum alloy used for the aluminum liner.
  • Chinese patent CN 115466887 A discloses "a high-strength and tough aluminum alloy liner material, preparation method, and application.”
  • a high-strength and tough aluminum alloy liner material preparation method, and application.
  • processes such as semi-continuous casting, homogenization heat treatment, reverse extrusion forming, annealing heat treatment, high-pressure spinning forming, neck spinning forming, and solution aging heat treatment
  • a high-strength and tough aluminum alloy liner for high-pressure hydrogen cylinders is prepared, significantly improving its mechanical properties.
  • reverse extrusion forming has the following disadvantages:
  • Reverse extrusion molding requires the use of special equipment and molds for production, and its production cost is higher than that of roll forming;
  • the material is more likely to have defects such as indentations, scratches and pores, and needs to undergo surface treatment to achieve good surface quality.
  • Chinese patent CN 114457265 B discloses "a high-strength and high-fatigue performance 6-series aluminum alloy, a gas cylinder, and a method for preparing the same.”
  • the alloy composition By optimizing the alloy composition, increasing the maximum solid solution of Mg2Si , and adding a homogenization heat treatment method, the base material grains after annealing are refined.
  • the resulting gas cylinder has a tensile strength of more than 340 MPa after spray quenching at 550-560°C and aging treatment at 160-165°C, and the number of fatigue cycles can reach more than 16,000 times.
  • This method has the following disadvantages: (1) This method adds a homogenization treatment process, which increases the cost for industrial production; (2) This method requires a cold rolling process, and the resulting plate has significant limitations and can only be used for the production of small-sized gas cylinders, which is not conducive to industrial promotion and application.
  • the current method of strengthening the inner liner of hydrogen storage cylinders mainly considers the use of aluminum tube strong spinning and reverse extrusion.
  • the only method of preparing aluminum alloy plates for hydrogen storage cylinders by rolling requires high-temperature and long-term homogenization heat treatment and cold rolling treatment.
  • the scope of application is small and is not conducive to industrial promotion.
  • the present invention aims to provide a high-strength and tough aluminum alloy plate for high-pressure hydrogen storage cylinder liners, a preparation method, and a cylinder liner.
  • the aluminum alloy plate has a yield strength of 54MPa or less, a tensile strength of 120MPa or less, and an elongation of 29% or more.
  • a hydrogen storage cylinder liner with high strength, toughness, and long fatigue life is obtained, with a yield strength of 305MPa or more, a tensile strength of 336MPa or more, and an elongation of 12.5% or more.
  • the burst strength is 144MPa or more, and the fatigue frequency is 14218 or more.
  • the aluminum alloy plate preparation method uses rolling hot deformation, which is time-consuming and low-cost, making it suitable for industrial application.
  • the present invention provides an aluminum alloy plate for a high-strength and tough high-pressure hydrogen storage cylinder liner.
  • the aluminum alloy plate further comprises the following chemical components in weight percentage: Mg: 0.93-1.14%, Si: 0.56-0.70%, Fe: 0.45-0.51%, Cu: 0.29-0.33%, Mn: 0.01-0.03%, Cr: 0.17-0.23%, Zn: 0.01-0.07%, Ti: 0.028-0.033%, Pb: 0.001-0.003%, Bi: 0.0002-0.0006%.
  • the aluminum alloy plate comprises the following components in weight percentage: Mg: 0.93-1.14%, Si: 0.56-0.70%, Fe: 0.45-0.51%, Cu: 0.29-0.33%, Mn: 0.01-0.03%, Cr: 0.17-0.23%, Zn: 0.01-0.07%, Ti: 0.028-0.033%, Pb: 0.001-0.003%, Bi: 0.0002-0.0006%, and the balance is Al and unavoidable impurities.
  • the grain structure of the aluminum alloy plate of the present invention is fine equiaxed grains, and the average grain size is (148-259) ⁇ (17-68) ⁇ m.
  • the numerical range after the " ⁇ " sign refers to the difference between the largest and smallest grains in the plate. The smaller the numerical range, the smaller the difference in grain size and the more uniform the grain size distribution.
  • the aluminum alloy plate of the present invention has a yield strength of ⁇ 54 MPa, a tensile strength of ⁇ 120 MPa, and an elongation of ⁇ 29%.
  • Mg can form a strengthening phase Mg 2 Si with Si to improve the strength of the alloy, but too high a content will reduce the toughness of the material. Therefore, the present invention controls the Mg element content to be 0.93-1.14%.
  • the present invention controls the Si content to be 0.56-0.70%.
  • the present invention controls the Cu content to be 0.29-0.33%.
  • Fe can generate inclusion substances when the pressure increases, thereby reducing the dissolution of the material in Al. Therefore, the Fe content is controlled within the range of 0.45-0.51% in the present invention.
  • Mn can be dissolved in aluminum alloys to hinder the occurrence of recrystallization. Too high a content will lead to severe intragranular segregation in the ⁇ phase, affecting the recrystallization process of the alloy and causing grain coarsening of the alloy in the annealed state.
  • the present invention controls the Mn content to 0.01-0.03% to avoid grain coarsening caused by intragranular segregation.
  • the present invention controls the Cr content to be 0.17-0.23%.
  • the present invention controls the Zn content to be 0.01-0.07%.
  • Ti can refine the grain structure, but too high a content will affect the ductility of the material. Therefore, the present invention controls the Ti content to be 0.028-0.033%.
  • Pb and Bi are harmful elements in gas cylinders and need to be strictly controlled.
  • the present invention strictly controls the Pb content to be 0.001-0.003%, and strictly controls the Bi content to be 0.0002-0.0006%.
  • the Mg2Si phase accounts for 1.2-1.4 mol% of the total microstructure phase and has a size of 0.8-1.5 ⁇ m
  • the Al2Cu phase accounts for 0.2-0.3 mol% of the total microstructure phase and has a size of 50-80nm, thereby improving the toughness and fatigue life of the gas cylinder liner.
  • the yield strength is ⁇ 305MPa
  • the tensile strength is ⁇ 336MPa
  • the elongation is ⁇ 12.5%.
  • the burst strength is ⁇ 144MPa
  • the fatigue frequency of the gas cylinder is ⁇ 14218 times
  • far exceeding the GB/T 35544 stipulates that the burst strength of the hydrogen storage cylinder liner is 78.75MPa and the fatigue frequency is 11,000 times.
  • the present invention provides a method for manufacturing the above-mentioned high-strength and high-pressure hydrogen storage cylinder liner aluminum alloy plate, comprising the following steps:
  • Heating temperature 420-500°C, heating time: 3-24h;
  • the hot rolled plate with a thickness of 12 to 30 mm is obtained by reversible hot rough rolling.
  • the maximum pass reduction rate is controlled to be above 35% during the hot rough rolling process, and the hot rolling finishing temperature is controlled to be 240 to 280°C.
  • the annealing temperature is 390-450° C.
  • the annealing time is 1-3 hours
  • the aluminum alloy plate is cooled to 200-260° C. at a cooling rate of 16-28° C./h, and then taken out of the furnace and air-cooled to room temperature to obtain the aluminum alloy plate.
  • air cooling refers to natural cooling in air, generally at a cooling rate of 30 to 50°C/h.
  • the thickness of the hot-rolled plate is 15 to 25 mm.
  • the annealing temperature is 410-430°C.
  • step 4 after annealing, the steel is cooled to 200-220° C. at a cooling rate of 18-22° C./h.
  • the present invention optimizes the pass reduction during hot rolling to ensure that the maximum pass reduction is ⁇ 35%, so that the fibrous structure in the aluminum alloy plate is fully broken and sufficient recrystallization nucleation cores are provided for the annealing process.
  • the hot rolling finishing temperature of the present invention is controlled at 240-280° C.
  • the hot rolling finishing temperature of the present invention is controlled at 240-280° C.
  • the plate After annealing, the plate is cooled to 200-260°C at a cooling rate of 16-28°C/h.
  • the aluminum alloy plate of the present invention contains elements such as Mg, Si, and Cu. Due to the quenching effect, if the cooling rate after annealing is too fast, strengthening phases such as Mg2Si and Al2Cu will be produced prematurely during the annealing process, which is not conducive to the deep drawing of the plate in the subsequent preparation of gas cylinders and reduces the alloy quenching effect during the heat treatment after deep drawing. Therefore, the cooling rate after annealing is controlled at 16-28°C/h in the present invention.
  • the present invention provides a high-strength, tough, and high-pressure hydrogen storage cylinder liner made from the above-mentioned aluminum alloy sheet, wherein the microstructure of the hydrogen storage cylinder liner includes a Mg2Si phase and an Al2Cu phase; wherein the Mg2Si phase accounts for 1.2 to 1.4 mol% of the total microstructure phase and has a size of 0.8 to 1.5 ⁇ m, and the Al2Cu phase accounts for 0.2 to 0.3 mol% of the total microstructure phase and has a size of 50 to 80 nm.
  • the yield strength of the inner liner of the hydrogen storage cylinder is ⁇ 305MPa, the tensile strength is ⁇ 336MPa, and the elongation is ⁇ 12.5%; under the testing standard of GB/T 35544, its bursting strength is ⁇ 144MPa, and the fatigue frequency is ⁇ 14218 times.
  • the present invention provides a method for manufacturing the above-mentioned high-strength and high-pressure hydrogen storage cylinder liner, comprising the following steps:
  • the aluminum alloy sheet is rounded to obtain a disc, the disc is oiled, cold drawn, the outer surface is polished, the lugs are cut, the end is spun, and the thread is made to obtain a preformed gas cylinder liner;
  • the obtained preformed gas cylinder liner is heated to 530-545°C for solution treatment within 40-80 minutes, and the solution treatment time is 40-80 minutes; after the solution treatment, it is cooled to room temperature with water and allowed to stand for 10-30 minutes; and then heated to 170-190°C within 30-60 minutes for aging treatment, and the aging time is 6-10 hours;
  • the outer surface of the heat-treated gas cylinder liner is wrapped with carbon fiber to obtain a finished gas cylinder liner.
  • the aluminum alloy sheet obtained above is used to prepare a hydrogen storage cylinder liner. Since the aluminum alloy composition optimizes the composition range of Mg, Si, and Cu elements and further controls Mg/Si to be 1.6-1.68, the precipitation of Mg2Si and Al2Cu strengthening phases is controlled during the subsequent T6 heat treatment process.
  • the molar content of the Mg2Si phase in the microstructure of the final cylinder is controlled to be 1.2-1.4%, and the size is 0.8-1.5 ⁇ m.
  • the molar content of the Al2Cu phase is controlled to be 0.2-0.3%, and the size is 50-80 nm. As a result, the obtained liner has high strength, thereby improving the burst performance of the cylinder.
  • the yield strength is ⁇ 305 MPa
  • the tensile strength is ⁇ 336 MPa
  • the elongation is ⁇ 12.5%.
  • the burst strength is ⁇ 144 MPa
  • the fatigue frequency is ⁇ 14218 times.
  • the present invention has the following beneficial effects:
  • This improves the toughness and fatigue life of the gas cylinder liner, and the yield strength is ⁇ 305MPa, the tensile strength is ⁇ 336MPa, and the elongation is ⁇ 12.5%.
  • the burst strength is ⁇ 144MPa
  • the fatigue frequency is ⁇ 14218 times, far exceeding the requirements of 78.75MPa and 11000 times for the hydrogen storage gas cylinder liner specified in GB/T35544.
  • the present invention optimizes the pass reduction during hot rolling to ensure a maximum pass reduction of 35% or greater, fully breaking up the fibrous structure in the aluminum alloy sheet and providing sufficient recrystallization nuclei during annealing.
  • the final rolling temperature during hot rolling is further optimized to 240-280°C, reducing the release of stored energy during hot rolling and providing sufficient driving force for recrystallization during annealing.
  • the quenching effect of the alloy is reduced and the grain structure of the alloy is improved. This not only improves the formability of the aluminum alloy sheet, but also contributes to the subsequent improvement of the toughness and fatigue life of the gas cylinder liner.
  • controlling the cooling rate during annealing prevents the premature precipitation of strengthening phases such as Mg2Si and Al2Cu during annealing, allowing them to precipitate after the subsequent T6 heat treatment. This improves the formability of the aluminum alloy sheet while ensuring the strength and toughness of the final gas cylinder.
  • the aluminum alloy sheet of the present invention is produced using a rolling hot deformation method, which avoids the need for prolonged heat treatment compared to traditional cold rolling processes.
  • This method also expands the thickness specifications of aluminum alloy sheet for gas cylinder liners, enabling the production of larger gas cylinders.
  • the aluminum alloy sheet of the present invention can be produced in a range of 12-30 mm. This facilitates industrialization and application, and compared to traditional aluminum tube strong spinning and reverse extrusion methods, this method eliminates the need for specialized equipment and molds, enabling high-volume, low-cost production and further facilitating industrialization and application.
  • FIG1 is a metallographic photograph of the aluminum alloy plate according to Example 1 of the present invention.
  • FIG2 is a metallographic photograph of the aluminum alloy plate of Example 2 of the present invention.
  • FIG3 is a metallographic photograph of the aluminum alloy plate of Example 3 of the present invention.
  • FIG4 is a metallographic photograph of the aluminum alloy plate of Example 4 of the present invention.
  • FIG5 is a metallographic photograph of the aluminum alloy plate of Example 5 of the present invention.
  • FIG6 is a metallographic photograph of the aluminum alloy plate of Example 6 of the present invention.
  • FIG7 is a metallographic photograph of the aluminum alloy plate of Comparative Example 1 of the present invention.
  • FIG8 is a metallographic photograph of the aluminum alloy plate of Comparative Example 2 of the present invention.
  • FIG9 is a metallographic photograph of the aluminum alloy plate of Comparative Example 3 of the present invention.
  • FIG10 is a metallographic photograph of the aluminum alloy plate of Comparative Example 4 of the present invention.
  • FIG11 is a metallographic photograph of the aluminum alloy plate of Comparative Example 5 of the present invention.
  • FIG12 is a metallographic photograph of the aluminum alloy plate of Comparative Example 6 of the present invention.
  • compositions of the aluminum alloy plates of the embodiments of the present invention and the comparative examples are shown in Table 1, and the remainder of the compositions includes Al and other inevitable impurities.
  • the aluminum alloy sheet obtained in the present invention is used to obtain the corresponding hydrogen storage cylinder liner according to the following steps:
  • the obtained preformed gas cylinder liner is heated to 530-545°C for solution treatment within 40-80 minutes, and the solution treatment time is 40-80 minutes; after the solution treatment, it is cooled to room temperature with water and allowed to stand for 10-30 minutes; and then heated to 170-190°C within 30-60 minutes for aging treatment, and the aging time is 6-10 hours;
  • the outer surface of the heat-treated gas cylinder liner is wrapped with carbon fiber to obtain a finished gas cylinder liner.
  • Table 4 shows the contents and sizes of Mg 2 Si and Al 2 Cu in the gas cylinder liner structures prepared from the aluminum alloy plates of the embodiments of the present invention and the comparative examples.
  • Example 1 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 1 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 1 of the present invention. It can be seen from the photograph that the grain structure is composed of equiaxed crystals with an average grain size of 148 ⁇ 17 ⁇ m, and there are only slight differences between the grain sizes.
  • the mechanical properties of the inner liner at room temperature were tested by sampling, and the yield strength was 310MPa, the tensile strength was 343MPa, and the elongation was 12.5%.
  • the burst strength of the hydrogen storage cylinder inner liner obtained can reach 150MPa, meeting the burst performance requirement of ⁇ 78.75MPa in GB/T 35544, and its fatigue frequency can reach 17131 times, meeting the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Example 2 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 2 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 2 of the present invention. As can be seen from the photograph, the grain structure is composed of equiaxed crystals with an average grain size of 237 ⁇ 46 ⁇ m.
  • the mechanical properties of the gas cylinder liner prepared using the same at room temperature are as follows: its yield strength is 308MPa, its tensile strength is 341MPa, and its elongation is 13.2%.
  • the obtained hydrogen storage gas cylinder liner has a burst strength of up to 146MPa, meeting the burst performance requirement of ⁇ 78.75MPa in GB/T 35544, and its fatigue frequency can reach 14314 times, meeting the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Example 3 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 3 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 3 of the present invention. It can be seen from the photograph that the grain structure is composed of equiaxed crystals with an average grain size of 232 ⁇ 68 ⁇ m.
  • the mechanical properties of the gas cylinder liner prepared using the same at room temperature are as follows: its yield strength is 305MPa, its tensile strength is 338MPa, and its elongation is 12.8%.
  • the obtained hydrogen storage gas cylinder liner has a burst strength of up to 144MPa, meeting the burst performance requirement of ⁇ 78.75MPa in GB/T 35544, and its fatigue frequency can reach 14532 times, meeting the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Example 4 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 4 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 4 of the present invention. As can be seen from the photograph, the grain structure is composed of equiaxed crystals with an average grain size of 203 ⁇ 43 ⁇ m.
  • the mechanical properties of the gas cylinder liner prepared using the same at room temperature are as follows: its yield strength is 306MPa, its tensile strength is 336MPa, and its elongation is 12.7%.
  • the obtained hydrogen storage gas cylinder liner has a burst strength of up to 145MPa, meeting the burst performance requirement of ⁇ 78.75MPa in GB/T 35544, and its fatigue frequency can reach 15135 times, meeting the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Example 5 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 5 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 5 of the present invention. As can be seen from the photograph, the grain structure is composed of equiaxed crystals with an average grain size of 204 ⁇ 38 ⁇ m.
  • the mechanical properties of the gas cylinder liner prepared using the same at room temperature are as follows: its yield strength is 309MPa, its tensile strength is 339MPa, and its elongation is 12.6%.
  • the obtained hydrogen storage gas cylinder liner has a burst strength of up to 148MPa, meeting the burst performance requirement of ⁇ 78.75MPa in GB/T 35544, and its fatigue frequency can reach 15157 times, meeting the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Example 6 samples were taken to test the grain structure and mechanical properties of the aluminum alloy plate after annealing.
  • the mechanical properties are shown in Table 3.
  • Figure 6 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Example 6 of the present invention. It can be seen from the photograph that the grain structure is composed of equiaxed crystals with an average grain size of 259 ⁇ 66 ⁇ m.
  • the mechanical properties of the gas cylinder liner prepared using it at room temperature are as follows: its yield strength is 308MPa, its tensile strength is 340MPa, and its elongation is 12.5%.
  • the obtained hydrogen storage gas cylinder liner has a burst strength of up to 147MPa, which meets the burst performance requirement of ⁇ 78.75MPa in GB/T 35544. Its fatigue frequency can reach 14218 times, which meets the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • Comparative Example 1 samples were taken to examine the grain structure and mechanical properties of the annealed aluminum alloy sheet.
  • the mechanical properties are shown in Table 3.
  • Figure 7 shows a micrograph of the rolled surface of the aluminum alloy sample from Comparative Example 1. The photograph shows an average grain size of 361 ⁇ 141 ⁇ m, coarse grains, and significant grain size variation.
  • the mechanical properties of the gas cylinder liner prepared using this material at room temperature showed a yield strength of 270 MPa, a tensile strength of 316 MPa, and an elongation of 15.4%.
  • the amount and particle size of the Mg2Si and Al2Cu strengthening phases in the resulting hydrogen storage cylinder liner microstructure did not meet the requirements of the present invention. Its burst strength was only 120 MPa, and its fatigue life was only 12,619 cycles.
  • FIG. 8 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Comparative Example 2 of the present invention. It can be seen from the photograph that the average grain size is 445 ⁇ 159 ⁇ m, the grain size is coarse, and the difference between the grain sizes is large.
  • the mechanical properties of the gas cylinder liner prepared using it at room temperature are as follows: its yield strength is 308MPa, its tensile strength is 339MPa, and its elongation is 12.9%.
  • the burst strength of the hydrogen storage gas cylinder liner obtained is 143MPa. Although it can reach the same level as the present invention, its fatigue frequency is lower, only 11318 times.
  • FIG. 9 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Comparative Example 3 of the present invention. It can be seen from the photograph that the average grain size is 549 ⁇ 245 ⁇ m, the grain size is coarse, and the difference between the grain sizes is large.
  • the mechanical properties of the gas cylinder liner prepared using it at room temperature are as follows: its yield strength is 307MPa, its tensile strength is 336MPa, and its elongation is 13.1%.
  • the burst strength of the hydrogen storage gas cylinder liner obtained is 144MPa.
  • the fatigue frequency of the hydrogen storage gas cylinder liner obtained is only 9532 times, which does not meet the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • FIG. 10 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Comparative Example 4 of the present invention. It can be seen from the photograph that the average grain size is 479 ⁇ 244 ⁇ m, the grain size is coarse, and the difference between the grain sizes is large.
  • the mechanical properties of the gas cylinder liner prepared using it at room temperature are as follows: its yield strength is 272MPa, its tensile strength is 315MPa, and its elongation is 13.5%.
  • the burst strength of the hydrogen storage gas cylinder liner obtained is low, at 123MPa. Its fatigue frequency is only 9613 times, which does not meet the fatigue performance requirement of ⁇ 11000 times in GB/T 35544.
  • FIG. 11 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Comparative Example 5 of the present invention. It can be seen from the photograph that the average grain size is 427 ⁇ 124 ⁇ m, the grain size is coarse, and the difference between the grain sizes is large.
  • the mechanical properties of the gas cylinder liner prepared using it at room temperature are as follows: its yield strength is 309MPa, its tensile strength is 338MPa, and its elongation is 12.4%.
  • the burst strength of the hydrogen storage gas cylinder liner obtained is 143MPa, but its fatigue frequency is relatively low, only 11639 times.
  • FIG. 12 is a metallographic structure photograph of the rolled surface of the aluminum alloy sample of Comparative Example 6 of the present invention. As can be seen from the photograph, the average grain size is 435 ⁇ 151 ⁇ m, the grain size is coarse, and the difference between the grain sizes is large.
  • the mechanical properties of the gas cylinder liner prepared using the same were tested at room temperature, and its yield strength was 273MPa, the tensile strength was 317MPa, and the elongation was 12.7%.
  • the obtained hydrogen storage gas cylinder liner had a low burst strength of 125MPa and a low fatigue frequency of only 11103 times.

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Abstract

一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆，其化学成分重量百分比为：Mg：0.93～1.14％，Si：0.56～0.70％，Fe：0.45～0.51％，Cu：0.29～0.33％，Mn：0.01～0.03％，Cr：0.17～0.23％，Zn：0.01～0.07％，Ti：0.028～0.033％，Pb：0.001～0.003％，Bi：0.0002～0.0006％，其余包括Al及其它不可避免的杂质，杂质总量≤0.15％，且上述元素还需要满足：Mg/Si＝1.6～1.68。本发明通过合金成分设计，并采用轧制热变形的方法，改善晶粒尺寸及Mg2Si、Al2Cu等强化相的分布，提高铝合金板材的成型性，获得高强韧性、高疲劳寿命的储氢气瓶内胆；而且，制备工艺耗时更短，成本更低，更加利于工业化推广及应用。

Description

一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆 技术领域
本发明涉及金属材料及其加工技术领域，具体涉及一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆。
背景技术
氢能作为清洁、高效、可持续新能源，成为低碳能源体系的主力之一，在能源、交通、工业生产领域，具有巨大市场潜力。氢能使用过程主要包括制氢、储存和运输、应用等方面，而氢能应用的关键是安全高效的氢能储运技术。
目前多使用钢瓶贮存氢燃料，但车用氢气钢瓶存在质量重、容重比小、易腐蚀、失效模式不安全，工作压力不高等缺点，制约了氢气能源在新能源汽车领域的应用。在提倡节能减排的背景下，新能源汽车亟需一种质量轻、耐高压、疲劳寿命高的储氢气瓶部件突破其应用瓶颈。
因此，为减轻质量，市场中出现了金属内胆纤维缠绕结构的储氢容器，金属内胆材料通常采用铝合金，但牌号为2xxx、7xxx等的高强韧铝合金旋压成形能力较弱，亟需一种成型能力强且强韧性高的铝合金材料，来制作储氢容器的金属内胆。
中国专利CN 112743878 A公开了“纤维复合材料高压储氢气瓶及其制备方法”，在6061铝制内胆外表面缠绕T700碳纤维，进而增强氢气瓶的强度和耐受性，提高氢气瓶对高压氢气贮存的性能和安全性，根据GB/T35544-2017标准进行测试，其爆破最终压力值可达170MPa以上，疲劳加载寿命可达10000次以上，与当前主流三型瓶的技术性能保持一致，获得了轻质高强、耐疲劳、结构刚度大、耐高低温冲击稳定性好的高压储氢气瓶，但该专利未提及铝制内胆所需铝材的相关技术。
中国专利CN 115382984 A公开了“一种大容积储氢气瓶铝合金内胆冲压方法及拉深模”，通过铝锭热冲压，然后进行车削，最后通过冷拉深成型，无需强旋减薄就能生产储氢气瓶铝合金内胆，有效解决了采用铝管强旋减薄加工大容积储氢气瓶铝合金内胆生产效率低的技术问题，但该专利未提及铝制内胆所用铝合金的相关技术。
中国专利CN 115466887 A公开了“一种高强韧铝合金内胆材料及制备方法、应用”，通过优化铝合金材料成分，采用半连续铸造、均匀化热处理、反挤压成形、退火热处理、强力旋压成形、收口旋压成形、固溶时效热处理等工序，制备出高压氢气瓶用高强韧铝合金内胆，使其力学性能得到显著提高。但相较于轧制成型，反挤压成型存在以下缺点：
(1)反挤压成型需要使用专门的设备和模具进行生产，相对于轧制成型，其生产成本更高；
(2)在反挤压成型过程中，由于材料需要穿过模口进行挤压，成品精度受到了模具的限制，而轧制成型可以通过多次轧制来提高产品的加工精度；
(3)相对于轧制成型在反挤压成型的过程中，材料容易出现压痕、划痕和气孔等缺陷，需要经过表面处理才能达到良好的表面质量。
中国专利CN 114457265 B公开了“一种高强度高疲劳性能6系铝合金、气瓶及其制备方法”，通过优化合金成分，提高Mg2Si的最大固溶量，增加均匀化热处理的方法，细化了退火后的基材晶粒；制得的气瓶在550-560℃下喷淋式淬火和160-165℃的时效处理后抗拉强度高达340MPa以上，疲劳循环次数可达16000次以上。但该方法存在以下缺点：(1)该方法增加了均匀化处理工艺，对于工业生产而言，增加成本；(2)该方法需经过冷轧工艺，得到的板材局限性较大，只能用于小规格的气瓶生产，不利于工业化的推广及应用。
综上所述，目前有关增强储氢气瓶内胆主要考虑采用铝管强旋及反挤压的方式进行制备，仅有的采用轧制方式制备储氢气瓶用铝合金板材的方法，需要通过高温长时的均匀化热处理以及冷轧轧制处理，可应用范围小，不利于工业化推广。
发明内容
本发明的目的在于提供一种高强韧高压储氢气瓶内胆用铝合金板材、制备方法及气瓶内胆，通过改善铝合金板材的晶粒尺寸及Mg2Si、Al2Cu等强化相的分布，提高铝合金板材的成型性，铝合金板材的屈服强度≤54MPa，抗拉强度≤120MPa，延伸率≥29％，进而获得高强韧性、高疲劳寿命的储氢气瓶内胆，其屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T35544的检测标准下，其爆破强度≥144MPa，疲劳频次≥14218次；铝合金板材制备方法采用轧制热变形，工艺耗时短、成本低，适合工业化应用。
为达到以上目的，本发明的技术方案如下：
在第一方面，本发明提供了一种高强韧高压储氢气瓶内胆用铝合金板材，除了Al和不可避免的杂质之外，所述铝合金板材还包含以下重量百分比计的化学成分：Mg：0.93～1.14％，Si：0.56～0.70％，Fe：0.45～0.51％，Cu：0.29～0.33％，Mn：0.01～0.03％，Cr：0.17～0.23％，Zn：0.01～0.07％，Ti：0.028～0.033％，Pb：0.001～0.003％，Bi：0.0002～0.0006％所述不可避免的杂质的总量≤0.15％，且上述元素还需要满足：Mg/Si＝1.6～1.68。
在本发明的一个实施方式中优选地，所述铝合金板材包含以重量百分比计的如下组分：Mg：0.93～1.14％，Si：0.56～0.70％，Fe：0.45～0.51％，Cu：0.29～0.33％，Mn：0.01～0.03％，Cr：0.17～0.23％，Zn：0.01～0.07％，Ti：0.028～0.033％，Pb：0.001～0.003％，Bi：0.0002～0.0006％，余量为Al和不可避免的杂质。
优选地，本发明所述铝合金板材的晶粒组织为细小的等轴晶，平均晶粒尺寸为(148～259)±(17～68)μm。
需要说明的是，“±”号之后的数值范围是指板材中的最大晶粒与最小晶粒之间的差值。该数值范围越小，则意味着晶粒尺寸之间的差异越小，晶粒尺寸分布越均匀。
本发明所述铝合金板材的屈服强度≤54MPa，抗拉强度≤120MPa，延伸率≥29％。
在本发明的成分设计中，
Mg可与Si形成强化相Mg2Si，提高合金的强度，但含量过高会降低材料的韧性，因此，本发明控制Mg元素含量在0.93～1.14％。
Si能增加强度，但是含量过高会造成材料腐蚀，因此，本发明控制Si含量在0.56～0.70％。
Cu能提高材料的强度和硬度，但含量过高也会造成材料腐蚀，因此，本发明控制Cu含量在0.29～0.33％。
Fe能在压力升高的时候产生包容物质，降低材料在Al中的溶解，因此，本发明控制Fe含量在0.45～0.51％。
Mn可固溶于铝合金中阻碍再结晶的发生，含量过高会导致在α相中产生严重的晶内偏析，影响合金的再结晶过程，造成合金在退火状态下晶粒粗化，本发明控制Mn含量在0.01～0.03％，避免因晶内偏析导致的晶粒粗化。
Cr能增加材料强度，控制晶粒大小，提供韧性，因此，本发明控制Cr含量在Cr：0.17～0.23％。
Zn能影响晶粒度和腐蚀性，因此，本发明控制Zn含量在0.01～0.07％。
Ti能够细化晶粒组织，但过高会影响材料延展性，因此，本发明控制Ti含量在0.028～0.033％。
Pb和Bi为气瓶中的有害元素，需严格控制，本发明严格控制Pb含量在0.001～0.003％，严格控制Bi含量在0.0002～0.0006％。
本发明在成分设计上，通过合金成分设计，并进一步控制Mg/Si＝1.6～1.68，控制由该铝合金板材制得的最终气瓶的微观组织中有Mg2Si、Al2Cu等强化相的析出，其中，Mg2Si相占微观组织相总量的1.2～1.4摩尔％，尺寸为0.8～1.5μm；Al2Cu相占微观组织相总量的0.2～0.3摩尔％，尺寸为50～80nm，提升气瓶内胆的强韧性和疲劳寿命，其屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T 35544的检测标准下，其爆破强度≥144MPa，气瓶疲劳频次≥14218次，远超GB/T 35544中规定的储氢气瓶内胆爆破强度为78.75MPa、疲劳频次11000次的需求。
在第二方面，本发明提供了上述高强韧高压储氢气瓶内胆用铝合金板材的制造方法，包括如下步骤：
1)冶炼、浇铸
按照上述的成分进行熔炼、铸造获得铸锭；
2)加热铸锭
加热温度：420～500℃，加热时间3～24h；
3)热轧
经可逆热粗轧获得12～30mm热轧板材，热粗轧过程中控制最大道次压下率在35％以上，热轧终轧温度控制在240～280℃；
4)退火
退火温度390～450℃，退火时间1～3h，退火结束后以16～28℃/h的冷却速率冷却至200～260℃，随后出炉空冷至室温，获得铝合金板材。
更具体地，“空冷”是指在空气中自然冷却，一般冷却速率为30～50℃/h。
优选地，步骤4)中，所述热轧板厚度为15～25mm。
优选地，步骤4)中，退火温度为410～430℃。
优选地，步骤4)中，退火结束后以18～22℃/h冷却速率冷却至200～220℃。
本发明通过优化热轧轧制过程中的道次压下量，保证最大道次压下量≥35％，使铝合金板材中的纤维状组织充分破碎，为退火过程提供足够的再结晶形核核心。
本发明热轧终轧温度控制在240～280℃，通过优化热轧轧制过程中的终轧温度，减少热轧过程中的储能释放，为后续退火过程提供足够的再结晶驱动力，细化铝合金的组织，形成铝合金板材的晶粒组织为细小的等轴晶，平均晶粒尺寸为(148～259)±(17～68)μm。
退火结束后以16～28℃/h的冷却速率冷却至200～260℃。本发明的铝合金板材存在Mg、Si、Cu等元素，由于淬火效应，如果板材退火结束后冷却速率过快，将会在退火过程中提前产生Mg2Si、Al2Cu等强化相，不利于板材后续制备气瓶过程中的深冲成型，减少在深冲成型后的热处理时的合金淬火效应的产生，因此，本发明退火后控制冷却速度在16～28℃/h。
在第三方面中，本发明提供了一种通过上述铝合金板材制得的高强韧高压储氢气瓶内胆，所述储氢气瓶内胆微观组织中包括Mg2Si相和Al2Cu相；其中，所述Mg2Si相占微观组织相总量的1.2～1.4摩尔％，尺寸为0.8～1.5μm，所述Al2Cu相占微观组织相总量的0.2～0.3摩尔％，尺寸为50～80nm。
优选地，所述储氢气瓶内胆的屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T 35544的检测标准下，其爆破强度≥144MPa，疲劳频次≥14218次。
在第四方面中，本发明提供了制造上述高强韧高压储氢气瓶内胆的方法，包括如下步骤：
1)气瓶成型
将铝合金板材落圆，制得圆片→圆片涂油→冷拉深→打磨外表面→切割制耳→旋压收口→制作螺纹，获得预成型气瓶内胆；
2)T6热处理
获得的预成型气瓶内胆在40～80min升温至530～545℃进行固溶，固溶时间40～80min；固溶后水冷至室温，静置10～30min；再在30～60min内升温至170～190℃进行时效处理，时效时间6～10h；
3)碳纤维缠绕
热处理后的气瓶内胆外表面缠绕碳纤维，获得成品气瓶内胆。
利用上述获得的铝合金板材制备储氢气瓶内胆，由于铝合金成分优化了Mg、Si、Cu元素的成分范围，并进一步控制Mg/Si＝1.6～1.68，在后续T6热处理过程中控制Mg2Si、Al2Cu强化相的析出，并控制最后气瓶的微观组织中Mg2Si相的摩尔含量为1.2～1.4％，尺寸为0.8～1.5μm，Al2Cu相的摩尔含量为0.2～0.3％，尺寸为50～80nm，从而使获得的内胆具有较高的强度，进而提升气瓶的爆破性能，其屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T35544的检测标准下，其爆破强度≥144MPa，疲劳频次≥14218次。
与现有技术相比，本发明的有益效果：
本发明在成分设计上，通过合金成分设计，并进一步控制Mg/Si＝1.6～1.68，控制铝合金板材在后续T6热处理中控制Mg2Si、Al2Cu等强化相的析出，使得最终气瓶微观组织中Mg2Si相的摩尔含量为1.2～1.4％，尺寸为0.8～1.5μm；Al2Cu相的摩尔含量为0.2～0.3％，尺寸为50～80nm，提升气瓶内胆的强韧性和疲劳寿命，其屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T35544的检测标准下，其爆破强度≥144MPa，疲劳频次≥14218次，远超GB/T35544中规定的储氢气瓶内胆爆破强度为78.75MPa、疲劳频次11000次的需求。
本发明在成分设计的基础上，通过优化热轧轧制过程中的道次压下量，保证最大道次压下量≥35％，使铝合金板材中的纤维状组织充分破碎，为退火过程提供足够的再结晶形核核心；进一步优化热轧轧制过程中的终轧温度范围为240～280℃，减少热轧过程中的储能释放，为退火过程提供足够的再结晶驱动力，再次通过控制退火过程中的冷却速度及出炉温度，减少合金淬火效应的产生，改善合金的晶粒组织，一方面可以提高铝合金板材的成型性，另一方面有助于后续气瓶内胆强韧性的提升以及气瓶内胆疲劳寿命的提升。且，在退火过程中冷却速度的控制，避免Mg2Si、Al2Cu等强化相在退火过程中提前析出，而在后续T6热处理后析出，在保证提高最终气瓶强韧性的基础上，提高了铝合金板材的成型性。
本发明铝合金板材的制备采用轧制热变形的方法，相较于传统冷轧工艺避免了长时间热处理，且拓展了气瓶内胆用铝合金板材的厚度规格，本发明铝合金板材的厚度可以在12-30mm，而传统的铝合金板材的厚度规格则在4mm左右，可用于更大规格气瓶生产，利于工业化推广及应用。相较于传统的铝管强旋及反挤压制备方法，无需专门的设备和模具，可进行大批量低成本生产，更加利于工业化推广及应用。
附图说明
图1为本发明实施例1铝合金板材的金相组织照片。
图2为本发明实施例2铝合金板材的金相组织照片。
图3为本发明实施例3铝合金板材的金相组织照片。
图4为本发明实施例4铝合金板材的金相组织照片。
图5为本发明实施例5铝合金板材的金相组织照片。
图6为本发明实施例6铝合金板材的金相组织照片。
图7为本发明对比例1铝合金板材的金相组织照片。
图8为本发明对比例2铝合金板材的金相组织照片。
图9为本发明对比例3铝合金板材的金相组织照片。
图10为本发明对比例4铝合金板材的金相组织照片。
图11为本发明对比例5铝合金板材的金相组织照片。
图12为本发明对比例6铝合金板材的金相组织照片。
具体实施方式
下面结合实施例和附图对本发明做进一步说明。
本发明实施例及对比例铝合金板材成分见表1，其成分余量包括Al及其它不可避免的杂质。
本发明实施例及对比例工艺参数见表2；
本发明实施例及对比例铝合金板材力学性能及晶粒尺寸见表3。
本发明获得的铝合金板材按照下述步骤获得对应的储氢气瓶内胆：
1)气瓶成型
铝合金板材落圆→圆片涂油→冷拉深→打磨外表面→切割制耳→旋压收口→制作螺纹，获得预成型气瓶内胆；
2)T6热处理
获得的预成型气瓶内胆在40～80min升温至530～545℃进行固溶，固溶时间40～80min；固溶后水冷至室温，静置10～30min；再在30～60min内升温至170～190℃进行时效处理，时效时间6～10h；
3)碳纤维缠绕
热处理后的气瓶内胆外表面缠绕碳纤维，获得成品气瓶内胆。
本发明实施例及对比例铝合金板材制备获得的气瓶内胆组织中包含的Mg2Si、Al2Cu含量及尺寸见表4。
本发明实施例及对比例铝合金板材制备获得的气瓶内胆力学性能、爆破强度及疲劳频次见表5，以GB/T 35544为检测标准。
实施例1，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图1为本发明实施例1铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为148±17μm，晶粒尺寸之间仅存在微小差异。取样检测内胆室温下的力学性能，其屈服强度为310MPa，抗拉强度为343MPa，延伸率为12.5％。获得的储氢气瓶内胆爆破强度可达150MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达17131次，满足GB/T 35544中≥11000次的疲劳性能要求。
实施例2，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图2为本发明实施例2铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为237±46μm。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为308MPa，抗拉强度为341MPa，延伸率为13.2％。获得的储氢气瓶内胆爆破强度可达146MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达14314次，满足GB/T 35544中≥11000次的疲劳性能要求。
实施例3，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图3为本发明实施例3铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为232±68μm。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为305MPa，抗拉强度为338MPa，延伸率为12.8％。获得的储氢气瓶内胆爆破强度可达144MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达14532次，满足GB/T 35544中≥11000次的疲劳性能要求。
实施例4，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图4为本发明实施例4铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为203±43μm。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为306MPa，抗拉强度为336MPa，延伸率为12.7％。获得的储氢气瓶内胆爆破强度可达145MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达15135次，满足GB/T 35544中≥11000次的疲劳性能要求。
实施例5，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图5为本发明实施例5铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为204±38μm。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为309MPa，抗拉强度为339MPa，延伸率为12.6％。获得的储氢气瓶内胆爆破强度可达148MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达15157次，满足GB/T 35544中≥11000次的疲劳性能要求。
实施例6，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图6为本发明实施例6铝合金样品轧面金相组织照片，从照片上可以看出，晶粒组织由等轴晶组成，平均晶粒尺寸为259±66μm。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为308MPa，抗拉强度为340MPa，延伸率为12.5％。获得的储氢气瓶内胆爆破强度可达147MPa，满足GB/T 35544中≥78.75MPa的爆破性能要求，其疲劳频次可达14218次，满足GB/T 35544中≥11000次的疲劳性能要求。
对比例1，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图7为本发明对比例1铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为361±141μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为270MPa，抗拉强度为316MPa，延伸率为15.4％。获得的储氢气瓶内胆微观组织中Mg2Si、Al2Cu强化相的数量及颗粒大小均不满足本发明要求，其爆破强度仅为120MPa，疲劳频次仅为12619次。
对比例2，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图8为本发明对比例2铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为445±159μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为308MPa，抗拉强度为339MPa，延伸率为12.9％。获得的储氢气瓶内胆爆破强度为143MPa，虽然能达到与本发明相同级别，但是其疲劳频次较低，仅为11318次。
对比例3，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图9为本发明对比例3铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为549±245μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为307MPa，抗拉强度为336MPa，延伸率为13.1％。获得的储氢气瓶内胆爆破强度为144MPa。获得的储氢气瓶内胆疲劳频次仅为9532次，不满足GB/T 35544中≥11000次的疲劳性能要求。
对比例4，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图10为本发明对比例4铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为479±244μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为272MPa，抗拉强度为315MPa，延伸率为13.5％。获得的储氢气瓶内胆爆破强度较低，为123MPa。其疲劳频次仅为9613次，不满足GB/T 35544中≥11000次的疲劳性能要求。
对比例5，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图11为本发明对比例5铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为427±124μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆室温下的力学性能，其屈服强度为309MPa，抗拉强度为338MPa，延伸率为12.4％。获得的储氢气瓶内胆爆破强度为143MPa，但是其疲劳频次较低，仅为11639次。
对比例6，取样检测退火后铝合金板材的晶粒组织及力学性能，力学性能见表3。图12为本发明对比例6铝合金样品轧面金相组织照片，从照片上可以看出，平均晶粒尺寸为435±151μm，晶粒尺寸粗大且晶粒尺寸之间差异较大。利用其制备的气瓶内胆检测室温下的力学性能，其屈服强度为273MPa，抗拉强度为317MPa，延伸率为12.7％。获得的储氢气瓶内胆爆破强度低，其爆破强度为125MPa，其疲劳频次较低，仅为11103次。




Claims (12)

  1. 一种储氢气瓶内胆用铝合金板材，其特征在于，除了Al和不可避免的杂质之外，所述铝合金板材还包含以下重量百分比计的化学成分：Mg：0.93～1.14％，Si：0.56～0.70％，Fe：0.45～0.51％，Cu：0.29～0.33％，Mn：0.01～0.03％，Cr：0.17～0.23％，Zn：0.01～0.07％，Ti：0.028～0.033％，Pb：0.001～0.003％，Bi：0.0002～0.0006％，所述不可避免的杂质的总量≤0.15％，且上述元素还需要满足：Mg/Si＝1.6～1.68。
  2. 如权利要求1所述的储氢气瓶内胆用铝合金板材，其特征在于，所述铝合金板材包含以重量百分比计的如下组分：Mg：0.93～1.14％，Si：0.56～0.70％，Fe：0.45～0.51％，Cu：0.29～0.33％，Mn：0.01～0.03％，Cr：0.17～0.23％，Zn：0.01～0.07％，Ti：0.028～0.033％，Pb：0.001～0.003％，Bi：0.0002～0.0006％，余量为Al和不可避免的杂质。
  3. 如权利要求1或2所述的储氢气瓶内胆用铝合金板材，其特征在于，所述铝合金板材的晶粒组织为等轴晶，平均晶粒尺寸为(148～259)±(17～68)μm。
  4. 如权利要求1或2所述的储氢气瓶内胆用铝合金板材，其特征在于，所述铝合金板材的厚度为12-30mm。
  5. 如权利要求1或2所述的储氢气瓶内胆用铝合金板材，其特征在于，所述铝合金板材的屈服强度≤54MPa，抗拉强度≤120MPa，延伸率≥29％。
  6. 制造如权利要求1～5中任一项所述储氢气瓶内胆用铝合金板材的方法，其特征在于，所述方法包括如下步骤：
    1)冶炼、浇铸
    按照权利要求1或2所述的成分进行熔炼、铸造获得铸锭；
    2)加热铸锭
    加热温度：420～500℃，加热时间2～24h；
    3)热轧
    经可逆热粗轧获得12～30mm热轧板材，热粗轧过程中控制最大道次压下量在35％以上，热轧终轧温度控制在240～280℃；
    4)退火
    退火温度390～450℃，退火时间1～3h，退火结束后以16～28℃/h的冷却速率冷却至200～260℃，随后出炉空冷至室温，获得铝合金板材。
  7. 如权利要求6所述的制造方法，其特征在于，步骤3)中，所述热轧板厚度为15～25mm。
  8. 如权利要求6所述的制造方法，其特征在于，步骤4)中，退火温度为410～430℃。
  9. 如权利要求6所述的制造方法，其特征在于，步骤4)中，退火结束后以18～22℃/h冷却速率冷却至200～220℃。
  10. 一种由权利要求1～5中任一项所述铝合金板材制备的储氢气瓶内胆，其特征在于，所述储氢气瓶内胆的微观组织包括Mg2Si相和Al2Cu相；其中，所述Mg2Si相占微观组织相总量的1.2～1.4摩尔％，尺寸为0.8～1.5μm，所述Al2Cu相占微观组织相总量的0.2～0.3摩尔％，尺寸为50～80nm。
  11. 如权利要求10所述的储氢气瓶内胆，其特征在于，所述储氢气瓶内胆的屈服强度≥305MPa，抗拉强度≥336MPa，延伸率≥12.5％；在GB/T35544的检测标准下，其爆破强度≥144MPa，疲劳频次≥14218次。
  12. 制造如权利要求10或11所述储氢气瓶内胆的方法，其特征在于，所述方法包括如下步骤：
    1)气瓶成型
    将铝合金板材落圆，制得圆片→圆片涂油→冷拉深→打磨外表面→切割制耳→旋压收口→制作螺纹，获得预成型气瓶内胆；
    2)T6热处理
    获得的预成型气瓶内胆在40～80min升温至530～545℃进行固溶，固溶时间40～80min；固溶后水冷至室温，静置10～30min；再在30～60min内升温至170～190℃进行时效处理，时效时间6～10h；
    3)碳纤维缠绕
    热处理后的气瓶内胆外表面缠绕碳纤维，获得成品气瓶内胆。
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CN108913925A (zh) * 2018-08-07 2018-11-30 中铝瑞闽股份有限公司 一种手机边框用6系合金阳极氧化铝板带材及其制备方法
CN115717207A (zh) * 2021-08-24 2023-02-28 宝山钢铁股份有限公司 一种用于硬质阳极氧化的6系铝合金及其制造方法
CN113883411A (zh) * 2021-08-31 2022-01-04 海鹰空天材料研究院(苏州)有限责任公司 一种铝合金内胆高压全缠绕气瓶及其制造方法
CN115466887A (zh) * 2022-09-16 2022-12-13 苏州轻装智能制造科技有限公司 一种高强韧铝合金内胆材料及制备方法、应用
CN117165821A (zh) * 2023-08-01 2023-12-05 天津忠旺铝业有限公司 一种氢能汽车储氢瓶用铝合金板材及其加工方法

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