WO2022127022A1 - 一种铝合金及其制备方法和应用 - Google Patents
一种铝合金及其制备方法和应用 Download PDFInfo
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- WO2022127022A1 WO2022127022A1 PCT/CN2021/094595 CN2021094595W WO2022127022A1 WO 2022127022 A1 WO2022127022 A1 WO 2022127022A1 CN 2021094595 W CN2021094595 W CN 2021094595W WO 2022127022 A1 WO2022127022 A1 WO 2022127022A1
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 193
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000001125 extrusion Methods 0.000 claims abstract description 58
- 238000010622 cold drawing Methods 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 238000000265 homogenisation Methods 0.000 claims description 50
- 230000032683 aging Effects 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 16
- 230000000171 quenching effect Effects 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 description 32
- 239000000203 mixture Substances 0.000 description 14
- 238000005728 strengthening Methods 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 6
- 238000005275 alloying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910016583 MnAl Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910016952 AlZr Inorganic materials 0.000 description 4
- 229910015136 FeMn Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- 238000013461 design Methods 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/04—Light metals
- C22C49/06—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/222—Inorganic material
- H01M50/224—Metals
-
- 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
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the technical field of alloys, and particularly relates to an aluminum alloy and a preparation method and application thereof.
- the power battery casing needs to have excellent corrosion resistance, medium and low temperature resistance, fast heat conduction, good welding performance and medium or high strength.
- the power battery casing usually adopts aluminum drawn square tubes or drawn aluminum barrels.
- 1000 series aluminum alloys have the advantages of high purity and easy extrusion due to their low strength, but they cannot meet the basic strength requirements of power battery casings; 3000 series aluminum alloys are aluminum alloys that cannot be strengthened by heat treatment.
- the cold working method can be used to improve the strength. When the deformation amount of cold working is large, the problem of breaking is easy to occur, and the mass production performance is low. The corners of the shell are prone to breakage and breakage.
- the current aluminum alloy cannot realize the production of thin-walled square shells on the basis of ensuring good strength and drawing performance, and it cannot meet the production and use requirements of power battery shells.
- the purpose of the present invention is to provide an aluminum alloy and a preparation method thereof.
- the aluminum alloy provided by the present invention has the characteristics of excellent extrusion performance, excellent cold drawing performance and high tensile strength, and can meet the requirements of thin-walled square shells. Requirements for strength and extrusion and cold drawing properties of profiles.
- the present invention provides an aluminum alloy, which, in terms of mass percentage, comprises the following elements:
- the mass ratio of Mn to Fe is (2.8-3.2): 1, and the total content of Mn and Fe is less than or equal to 1.45wt.%.
- the content of a single element in the unavoidable impurities is ⁇ 0.05%, and the total content of the unavoidable impurities is ⁇ 0.15%.
- the inevitable impurities include one or more of V, Ca and Na.
- the tensile strength of the aluminum alloy is 180-200 MPa.
- the limit wall thickness is 0.55mm, and the limit circumcircle diameter of the square section profile is 140mm;
- the limit wall thickness is 0.4mm, and the limit circumcircle diameter of the square section profile is 138.5mm.
- the present invention also provides the preparation method of the aluminum alloy described in the above technical solution, comprising the following steps:
- the alloy raw materials are sequentially smelted and cast to obtain an aluminum alloy ingot
- the aluminum alloy ingot is sequentially subjected to homogenization treatment, extrusion treatment, quenching, aging treatment and cold drawing to obtain the aluminum alloy.
- the temperature of the smelting is 740-780° C., and the time is 2-4 hours.
- the casting temperature is 690-740°C.
- the homogenization treatment includes a first homogenization treatment, a second homogenization treatment and a third homogenization treatment performed in sequence;
- the holding temperature of the first homogenization treatment is 520-540° C., and the holding time is 2-4 hours;
- the holding temperature of the second homogenization treatment is 580-600° C., and the holding time is 6-10 h;
- the holding temperature of the third homogenization treatment is 460-480° C., and the holding time is 2-4 hours.
- the holding temperature of the first homogenization treatment is obtained by heating at room temperature, and the heating rate is 2-5°C/min.
- the holding temperature of the second homogenization treatment is obtained by raising the temperature of the holding temperature of the first homogenization treatment; the heating rate is 2-5°C/min.
- the holding temperature of the third homogenization treatment is obtained by cooling the holding temperature of the second homogenization treatment; the cooling rate is 0.5-2°C/min.
- the temperature of the extrusion treatment is 460-520° C., and the extrusion ratio is 30-150.
- the cooling rate of the quenching is greater than or equal to 100°C/min.
- the holding temperature of the aging treatment is 150-170° C., and the holding time is 1-3 h.
- the holding temperature of the aging treatment is obtained by heating at room temperature; the heating rate is 3-10° C./min.
- the cold drawing is one-time cold drawing, and the deformation amount of the cold drawing is 15-30%.
- the present invention also provides the application of the aluminum alloy described in the above technical solution or the aluminum alloy prepared by the preparation method described in the above technical solution as a thin-walled square shell profile in a battery casing.
- the present invention also provides a square shell, which is prepared from the aluminum alloy described in the above technical solution or the aluminum alloy obtained by the preparation method described in the above technical solution, and the preparation method includes extrusion or cold drawing;
- the wall thickness of the square shell obtained by extrusion is 0.50-0.65mm;
- the wall thickness of the square shell obtained by cold drawing is 0.40-0.50 mm.
- the invention provides an aluminum alloy, which in terms of mass percentage, comprises the following elements: Cu 0.10-0.18%, Fe 0.33-0.38%, Mn 1.05-1.10%, Si 0.06-0.18%, Mg 0.10-0.20%, Zr 0.04 ⁇ 0.07%, Cr 0.03 ⁇ 0.05%, Ti ⁇ 0.03%, the balance of Al and inevitable impurities; the mass ratio of Mn to Fe is (2.8 ⁇ 3.2): 1, and the total content of Mn and Fe ⁇ 1.45 wt.%.
- Al provides the matrix alloy element; Mn is the main alloy element, Mn and Al form MnAl 6 phase, and the addition of Mn is conducive to the spheroidization of Fe phase hard particles, which is beneficial to improve the extrusion processability of the alloy; Cu It is beneficial to improve the strength of aluminum alloys; Mg is beneficial to refine the grain size of aluminum alloys and improve the strength; Fe is beneficial to the formation of (FeMn)Al 6 phase, which can effectively refine the grains of aluminum alloys; Al, Si and Mn can form The ternary phase Al 12 Mn 3 Si 2 , when the ternary phase Al 12 Mn 3 Si 2 dissolves Fe, the quaternary phase AlFeMnSi will be formed.
- the present invention controls the content of Fe and Si to ensure that on the basis of forming the ternary phase and the quaternary phase, Fe and Si can still play a role in grain refinement or solid solution strengthening of aluminum alloys; Cu, Si and Mg all play a role in solid solution strengthening, and Si and Mg can precipitate Mg 2 Si strengthening phase, which is beneficial to enhance the strength of aluminum alloys.
- Strength; Zr and Cr are micro-alloying elements of aluminum alloys, and AlCr 7 and AlZr 3 formed by Zr, Cr and Al are thermodynamically stable fine dispersed phases, which are beneficial to inhibit the recrystallization and grain growth of aluminum alloys; Ti is beneficial to refine the cast grains.
- Mn is controlled at 1.05-1.10wt.%, which is beneficial to improve the plasticity, weldability, heat resistance and corrosion resistance of aluminum alloys, while avoiding large extrusion deformation resistance and serious deterioration of extrusion performance;
- Si Mg Controlling the content of Cu and Cu within the corresponding content range is conducive to ensuring the strength of the aluminum alloy, and at the same time avoiding the large extrusion deformation resistance of the aluminum alloy, preventing the deterioration of the extrusion performance, and also ensuring the formation of Mg 2 Si strengthening phase and avoiding the favorable influence of Fe.
- controlling the content of Zr and Cr is beneficial to ensure that the aluminum alloy has a fibrous grain structure, preventing the formation of a mixed grain structure in which a coarse recrystallized structure and a fibrous grain structure coexist, and avoiding the deterioration of the strength and extrusion properties of the aluminum alloy;
- Controlling the relationship between the content of Mn and Fe is beneficial to avoid the formation of a large number of coarse flakes (FeMn)Al 6 , to prevent the reduction of the ductility of the aluminum alloy, and to balance the relationship between the strength and extrudability of the aluminum alloy to meet the needs of thin-walled aluminum alloys. Requirements for strength and crush performance of square shells.
- the test results of the examples show that the tensile strength of the aluminum alloy provided by the present invention is 182-200 MPa; the surface of the extruded product after extrusion is smooth (the extruded product is a square shell with a wall thickness of 0.5-0.65 mm and a circumscribed circle of 128 mm directly), Excellent extrusion performance; after cold-drawing, the surface of the cold-drawn product is smooth (the cold-drawn product is a square shell with a wall thickness of 0.4-0.5mm, and the circumscribed circle is directly 128mm), and the cold-drawn performance is excellent.
- the invention also provides a method for preparing an aluminum alloy, comprising the following steps: sequentially smelting and casting alloy raw materials to obtain an aluminum alloy ingot; and sequentially performing homogenization treatment, extrusion treatment and quenching on the aluminum alloy ingot , aging treatment and cold drawing to obtain the aluminum alloy.
- the homogenization treatment is beneficial to eliminate the macro- and micro-segregation of alloying elements in the ingot, so that the alloying elements and the coarse compounds are fully solid-dissolved, and at the same time, fine dispersions are formed; the aging treatment helps to make the strengthening phase ( Mg 2 Si) is precipitated to improve the strength of the aluminum alloy.
- Fig. 1 is the preparation method flow chart of aluminum alloy in the present invention
- Example 2 is a metallographic diagram of an aluminum alloy in Example 1;
- Fig. 3 is the EBSD photo of aluminum alloy in embodiment 1;
- Fig. 4 is the SEM image of aluminum alloy in embodiment 1;
- Fig. 5 is the EDS figure of the aluminum alloy in embodiment 1;
- Figure 6 is a dimensional drawing of the sample in the extrusion test
- Figure 7 is a dimensional drawing of the specimen in the cold drawing test.
- the invention provides an aluminum alloy, which is characterized in that, in terms of mass percentage, it includes the following elements:
- the mass ratio of Mn to Fe is (2.8-3.2): 1, and the total content of Mn and Fe is less than or equal to 1.45wt.%.
- the aluminum alloy of the present invention includes 0.10-0.18% of Cu, preferably 0.11-0.17%, more preferably 0.12-0.16%.
- Cu has the effect of solid solution strengthening, which is beneficial to improve the strength of the aluminum alloy;
- Cu is controlled within the content range, which is beneficial to ensure the strength of the aluminum alloy, and at the same time avoids the aluminum alloy from being large in extrusion deformation resistance and prevents extrusion performance. deterioration.
- the aluminum alloy of the present invention includes 0.33-0.38% Fe, preferably 0.335-0.375%, more preferably 0.34-0.37%.
- Fe is beneficial to the formation of (FeMn)Al 6 phase, which can effectively refine the grains of the aluminum alloy.
- the aluminum alloy of the present invention includes 1.05-1.10% of Mn, preferably 1.055-1.095%, more preferably 1.06-1.09%.
- Mn is the main alloying element
- Mn and Al form MnAl 6 phase
- Mn is beneficial to the spheroidization of Fe phase hard particles, which is beneficial to improve the extrusion processability of the alloy
- Mn is controlled at 1.05-1.10 wt.%, which is beneficial to improve the plasticity, weldability, heat resistance and corrosion resistance of the aluminum alloy, and at the same time avoids large extrusion deformation resistance and prevents the serious deterioration of extrusion performance.
- the aluminum alloy of the present invention includes 0.06-0.18% of Si, preferably 0.07-0.17%, more preferably 0.08-0.16%.
- Si has the effect of solid solution strengthening, and Al, Si and Mn can form a ternary phase Al 12 Mn 3 Si 2 .
- the ternary phase Al 12 Mn 3 Si 2 dissolves Fe, it will form a quaternary phase AlFeMnSi.
- the aluminum alloy of the present invention includes 0.10-0.20% of Mg, preferably 0.11-0.19%, more preferably 0.12-0.18%.
- Mg has the effect of solid solution strengthening, which is beneficial to refine the grain size of the aluminum alloy and improve the strength; moreover, Si and Mg can precipitate the Mg 2 Si strengthening phase, which is beneficial to enhance the strength of the aluminum alloy; and Mg are controlled within the corresponding content range, which is beneficial to ensure the strength of the aluminum alloy, and at the same time avoid the extrusion deformation resistance of the aluminum alloy from being large, prevent the deterioration of the extrusion performance, and also ensure the formation of Mg 2 Si strengthening phase, so as to avoid weakening the advantages of Fe. influences.
- the aluminum alloy of the present invention includes 0.04-0.07% of Zr, preferably 0.045-0.065%, more preferably 0.05-0.06%.
- Zr is a micro-alloying element of aluminum alloy
- AlZr 3 formed by Zr and Al is a thermodynamically stable fine dispersion phase, which is beneficial to inhibit the recrystallization and grain growth of aluminum alloy; control the content of Zr , which is beneficial to ensure that the aluminum alloy has a fibrous grain structure, prevent the formation of a mixed grain structure in which a coarse recrystallized structure and a fibrous grain structure coexist, and avoid the deterioration of the strength and extrusion performance of the aluminum alloy.
- the aluminum alloy of the present invention includes 0.03-0.05% of Cr, preferably 0.033-0.048%, more preferably 0.035-0.045%.
- Cr is a microalloying element of aluminum alloy
- AlCr7 formed by Cr and Al is a thermodynamically stable fine disperse phase, which is beneficial to inhibit recrystallization and grain growth of aluminum alloy. Controlling the content of Cr is beneficial to ensure that the aluminum alloy has a fibrous grain structure, prevent the formation of a mixed grain structure in which a coarse recrystallized structure and a fibrous grain structure coexist, and avoid the deterioration of the strength and extrusion performance of the aluminum alloy.
- the aluminum alloy of the present invention includes Ti ⁇ 0.03%, preferably 0.001-0.028%, more preferably 0.01-0.02%.
- Ti is beneficial to the refinement of the cast grains.
- the aluminum alloy of the present invention includes the balance of Al and inevitable impurities.
- Al is a matrix alloying element.
- the content of a single element in the unavoidable impurities is preferably ⁇ 0.05%, more preferably ⁇ 0.03%, more preferably ⁇ 0.01%; the total content of the unavoidable impurities is preferably ⁇ 0.05% ⁇ 0.15%, more preferably ⁇ 0.1%, still more preferably ⁇ 0.05%.
- the unavoidable impurities preferably include one or more of V, Ca and Na.
- the mass ratio of Mn to Fe is (2.8-3.2):1, preferably (2.85-3.15):1, more preferably (2.9-3.1):1; the total content of Mn and Fe is preferably ⁇ 1.45 wt.%, more preferably ⁇ 1.40%.
- controlling the content relationship between Mn and Fe is beneficial to avoid the formation of a large number of coarse flakes (FeMn)Al 6 , to prevent the reduction of the ductility of the aluminum alloy, and to balance the relationship between the strength and extrudability of the aluminum alloy, Meet the strength and extrusion performance requirements of thin-walled square shell profiles.
- the tensile strength of the aluminum alloy is preferably 180-200 MPa.
- the limit wall thickness is preferably 0.55mm, and the limit circumscribed circle diameter of the square section profile is preferably 140mm.
- the limit wall thickness is preferably 0.4mm, and the limit circumcircle diameter of the square section profile is preferably 138.5mm.
- the present invention also provides the preparation method of the aluminum alloy described in the above technical solution, comprising the following steps:
- the alloy raw materials are sequentially smelted and cast to obtain an aluminum alloy ingot
- the aluminum alloy ingot is sequentially subjected to homogenization treatment, extrusion treatment, quenching, aging treatment and cold drawing to obtain the aluminum alloy.
- FIG. 1 is a flow chart of the preparation method of the aluminum alloy in the present invention, and the preparation method of the aluminum alloy provided by the present invention will be described in detail below with reference to FIG. 1 .
- the alloy raw materials are sequentially smelted and cast to obtain an aluminum alloy ingot.
- the present invention does not specifically limit the alloy raw material, and any alloy raw material that can satisfy the composition of the aluminum alloy elements for the thin-walled square shell can be used.
- the smelting temperature is preferably 740-780°C, more preferably 750-760°C; the smelting time is preferably 2-4h, more preferably 2-3h.
- the smelting equipment is preferably a tilting melting furnace.
- the temperature of the casting is preferably 690 to 740°C, and more preferably 700 to 720°C.
- the present invention sequentially performs homogenization treatment, extrusion treatment, quenching, aging treatment and cold drawing on the aluminum alloy ingot to obtain the aluminum alloy for the thin-walled square shell.
- the aluminum alloy ingot is subjected to homogenization treatment to obtain the homogenized ingot.
- the homogenization treatment preferably includes a first homogenization treatment, a second homogenization treatment, and a third homogenization treatment, which are sequentially performed.
- the homogenization treatment is beneficial to eliminate the macro and micro segregation of alloy elements in the ingot, so that the alloy elements and the coarse compounds are fully dissolved, and at the same time, fine dispersions are formed.
- the holding temperature of the first homogenization treatment is preferably 520-540°C, more preferably 525-535°C; the holding time is preferably 2-4h, more preferably 2.5-3.5h.
- the holding temperature of the first homogenization treatment is preferably obtained by heating at room temperature; the heating rate is preferably 2-5°C/min, more preferably 3-4°C/min.
- the first homogenization treatment is beneficial to completely eliminate the macro and micro segregation of Si, Mg, and Cu elements inside the ingot.
- the holding temperature of the second homogenization treatment is preferably 580-600°C, more preferably 585-595°C; the holding time is preferably 6-10 h, more preferably 6.5-9.5 h.
- the holding temperature of the second homogenization treatment is preferably obtained by raising the temperature of the holding temperature of the first homogenization treatment; the heating rate is preferably 2-5°C/min, more preferably 3-4°C/min. min.
- the second homogenization treatment is conducive to promoting the spheroidization of Fe phase and re-solid solution of the high-temperature precipitation phase precipitated by the first homogenization treatment, so as to prepare for the subsequent third-stage precipitation.
- the holding temperature of the third homogenization treatment is preferably 460-480°C, more preferably 465-475°C; the holding time is preferably 2-4h, more preferably 2.5-3.5h.
- the holding temperature of the third homogenization treatment is preferably obtained by cooling the holding temperature of the second homogenization treatment; the cooling rate is preferably 0.5-2°C/min, more preferably 1-1.5°C/min. min.
- the third homogenization treatment is beneficial to ensure that the high-temperature precipitation phases AlCr 7 , AlZr 3 , and MnAl 6 are sufficiently and finely dispersed and precipitated.
- the parameters of the homogenization treatment are not within the parameters described in the present invention, the deformation resistance of the aluminum alloy will be too large, the extrusion will be difficult, and the coexistence of fibrous crystals and coarse crystal grains will be formed in the subsequent extrusion treatment process.
- the mixed crystal state greatly affects the strength of aluminum alloy products.
- the present invention preferably cools the obtained homogenized ingot to room temperature; the cooling is preferably air cooling.
- the present invention sequentially performs extrusion treatment and quenching on the homogenized ingot to obtain a deformed aluminum alloy.
- the temperature of the extrusion treatment is preferably 460 to 520°C, more preferably 465 to 515°C.
- the temperature of the extrusion treatment is preferably obtained by increasing the temperature at room temperature; the present invention does not specifically limit the rate of temperature increase, and any rate of temperature increase may be used.
- the extrusion ratio of the extrusion treatment is preferably 30-150, and more preferably 40-80.
- the extrusion processing equipment is preferably a forward single-action extruder.
- the extrusion treatment is beneficial to realize the solid solution of the alloy strengthening phase, and the extrusion treatment combined with the extrusion die can obtain a prototype of the product, which is beneficial to the realization of precise process control.
- the quenching is preferably in-line air-cooled quenching.
- the cooling rate of the quenching is preferably ⁇ 100°C/min, more preferably 100-120°C/min.
- the quenching facilitates the retention of Mg and Si in the product as supersaturated solid solutions.
- the present invention After obtaining the deformed aluminum alloy, the present invention performs aging treatment on the deformed aluminum alloy to obtain an aging aluminum alloy.
- the holding temperature of the aging treatment is preferably 150-170°C, more preferably 155-165°C; the holding time is preferably 1-3h, more preferably 1.5-2.5h.
- the temperature of the aging treatment is preferably obtained by heating at room temperature; the heating rate is preferably 3-10°C/min, more preferably 7-10°C/min.
- the aging treatment helps to precipitate the strengthening phase (Mg 2 Si) in the aluminum alloy and improves the strength of the aluminum alloy; within the condition range of the aging treatment described in the present invention, it is beneficial to ensure the aluminum alloy at the same time Strength and drawing ability to prevent the reduction of aluminum alloy strength or the occurrence of drawing difficulties.
- the present invention draws the aging aluminum alloy to obtain the aluminum alloy.
- the cold drawing is preferably a single cold drawing.
- the deformation amount of the cold drawing is preferably 15 to 30%, and more preferably 18 to 28%.
- the drawing is favorable for cooperating with aging treatment to synergistically improve the strength, extrusion performance and drawing performance of the aluminum alloy; meanwhile, it is favorable for ensuring the formability of the thin-walled square shell of the aluminum alloy.
- the present invention also provides the application of the aluminum alloy described in the above technical solution or the aluminum alloy prepared by the preparation method described in the above technical solution as a thin-walled square shell profile in a battery casing.
- the application is preferably to use the aluminum alloy directly as a profile alloy, to form a thin-walled square shell profile, and to use the thin-walled square shell profile obtained by forming as a battery shell.
- the elemental composition of the designed aluminum alloy is Cu 0.10%, Fe 0.33%, Mn 1.05%, Si 0.06%, Mg 0.10%, Zr 0.04%, Cr 0.03%, Ti 0.02%, the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- Preparation of aluminum alloy The alloy raw material conforming to the design element composition is smelted at 750°C for 3 hours, and the obtained melt is cast at 710°C to obtain an aluminum alloy ingot;
- the aluminum alloy ingot was heated to 530°C at a rate of 3.5°C/min, kept at 530°C for 3 hours, then heated to 580°C at a rate of 3.5°C/min, kept at 580°C for 8 hours, and then kept at 580°C for 8 hours.
- the temperature was lowered to 460°C at a rate of 1.0°C/min, kept at 460°C for 2 hours, and air-cooled to room temperature to obtain a homogenized ingot; then the obtained homogenized ingot was heated to 480°C and then extruded.
- the extrusion ratio was 50, and then conduct online air-cooling quenching at a cooling rate of 100 °C/min to obtain a deformed aluminum alloy; heat the obtained deformed aluminum alloy to 150 °C at a rate of 5 °C/min, and keep it at 150 °C for 2 hours for aging treatment , to obtain an aging aluminum alloy; the obtained aging aluminum alloy is subjected to primary cold drawing with a deformation amount of 25% to obtain the aluminum alloy.
- Example 1 The aluminum alloy obtained in Example 1 was observed with a metallographic microscope, and the obtained metallographic diagram was shown in FIG. 2 .
- the electron backscatter diffraction test was performed on the aluminum alloy obtained in Example 1, and the obtained EBSD photo was shown in FIG. 3 . It can be seen from FIGS. 2 to 3 that the aluminum alloy provided by the present invention has fine grains and has a fibrous crystal structure.
- Example 1 A scanning electron microscope test was performed on the aluminum alloy obtained in Example 1, and the obtained SEM image was shown in FIG. 4 .
- the insoluble primary secondary phase spheroidized white particles in the figure
- MgSi there is no soluble secondary phase MgSi
- the high temperature precipitation phases AlCr 7 , AlZr 3 and MnAl 6 are uniform. diffuse distribution.
- X-ray energy spectrum analysis was performed on the "spectrum 1" site in Fig. 4, and the obtained EDS diagram was shown in Fig. 5. It can be seen from Fig. 5 that the "spectrum 1" site in Fig. 4 mainly contains Mn and Al, forming a MnAl 6 precipitation phase.
- the elemental composition of the designed aluminum alloy is Cu 0.18%, Fe 0.38%, Mn 1.10%, Si 0.18%, Mg 0.20%, Zr 0.07%, Cr 0.05%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the aluminum alloy ingot was heated to 530°C at a rate of 3.5°C/min, kept at 530°C for 3 hours, then heated to 580°C at a rate of 3.5°C/min, kept at 580°C for 8 hours, and then kept at 580°C for 8 hours.
- the temperature was lowered to 460°C at a rate of 1.0°C/min, kept at 460°C for 2 hours, and air-cooled to room temperature to obtain a homogenized ingot; then the obtained homogenized ingot was heated to 480°C and then extruded.
- the extrusion ratio was 40, and then conduct online air-cooling quenching at a cooling rate of 100 °C/min to obtain a deformed aluminum alloy; heat the obtained deformed aluminum alloy to 150 °C at a rate of 5 °C/min, and keep at 150 °C for 2 hours for aging treatment , to obtain an aging aluminum alloy; the obtained aging aluminum alloy is subjected to primary cold drawing with a deformation amount of 25% to obtain the aluminum alloy.
- the elemental composition of the designed aluminum alloy is Cu 0.15%, Fe 0.38%, Mn 1.07%, Si 0.10%, Mg 0.17%, Zr 0.05%, Cr 0.05%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- Preparation of aluminum alloy The alloy raw material conforming to the design element composition is smelted at 750°C for 3 hours, and the obtained melt is cast at 710°C to obtain an aluminum alloy ingot;
- the aluminum alloy ingot was heated to 530°C at a rate of 3°C/min, kept at 530°C for 3 hours, then heated to 580°C at a rate of 3°C/min, kept at 580°C for 8 hours, and then kept at 580°C for 8 hours.
- the temperature was lowered to 460°C at a rate of 0.8°C/min, kept at 460°C for 2 hours, and air-cooled to room temperature to obtain a homogenized ingot; then the obtained homogenized ingot was heated to 480°C and then extruded.
- the extrusion ratio was 30, and then conduct online air-cooling and quenching at a cooling rate of 100 °C/min to obtain a deformed aluminum alloy; the obtained deformed aluminum alloy is heated to 150 °C at a rate of 5 °C/min, and is maintained at 150 °C for 2 hours for aging treatment , to obtain an aging aluminum alloy; the obtained aging aluminum alloy is subjected to primary cold drawing with a deformation amount of 25% to obtain the aluminum alloy.
- the elemental composition of the designed aluminum alloy is Cu 0.12%, Fe 0.34%, Mn 1.05%, Si 0.09%, Mg 0.16%, Zr 0.04%, Cr 0.03%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the aluminum alloy ingot was heated to 530°C at a rate of 3.5°C/min, kept at 530°C for 3 hours, then heated to 580°C at a rate of 3.5°C/min, kept at 580°C for 8 hours, and then kept at 580°C for 8 hours.
- the temperature was lowered to 460°C at a rate of 1.0°C/min, kept at 460°C for 2 hours, and air-cooled to room temperature to obtain a homogenized ingot; then the obtained homogenized ingot was heated to 480°C and then extruded.
- the extrusion ratio was 50, and then conduct online air-cooling quenching at a cooling rate of 100 °C/min to obtain a deformed aluminum alloy; heat the obtained deformed aluminum alloy to 150 °C at a rate of 5 °C/min, and keep it at 150 °C for 2 hours for aging treatment , to obtain an aging aluminum alloy; the obtained aging aluminum alloy is subjected to primary cold drawing with a deformation amount of 25% to obtain the aluminum alloy.
- the elemental composition of the designed aluminum alloy is Cu 0.15%, Fe 0.30%, Mn 1.06%, Si 0.10%, Mg 0.17%, Zr 0.02%, Cr 0.02%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the preparation method of the aluminum alloy is the same as that in Example 1, and the aluminum alloy is obtained.
- the elemental composition of the designed aluminum alloy is Cu 0.15%, Fe 0.38%, Mn 1.07%, Si 0.10%, Mg 0.17%, Zr 0.05%, Cr 0.05%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the uniform treatment is as follows: the aluminum alloy ingot is heated to 530°C at a rate of 3°C/min, kept at 530°C for 3 hours, and then heated to 580°C at a rate of 3°C/min, and Heat preservation at 580° C. for 8 hours, air-cooled to room temperature, to obtain a homogenized ingot; other technical means are the same as those in Example 3, to obtain an aluminum alloy.
- the elemental composition of the designed aluminum alloy is Cu 0.15%, Fe 0.38%, Mn 1.07%, Si 0.10%, Mg 0.17%, Zr 0.05%, Cr 0.05%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the elemental composition of the designed aluminum alloy is Cu 0.15%, Fe 0.38%, Mn 1.07%, Si 0.10%, Mg 0.17%, Zr 0.05%, Cr 0.05%, Ti 0.02%, and the balance of Al and unavoidable impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the uniform treatment is as follows: the aluminum alloy ingot is heated to 530°C at a rate of 3°C/min, kept at 530°C for 3 hours, and then heated to 560°C at a rate of 3°C/min, and The temperature was kept at 560 °C for 8 h, then cooled to 460 °C at a rate of 0.8 °C/min, and kept at 460 °C for 2 h, and air-cooled to room temperature to obtain a homogenized ingot; other technical means were the same as in Example 3, and an aluminum alloy was obtained. .
- the elemental composition of the designed aluminum alloy is Cu 0.10%, Fe 0.33%, Mn 1.05%, Si 0.06%, Mg 0.10%, Cr 0.10%, Ti 0.02%, the balance of Al and inevitable Impurities; the individual content of unavoidable impurities is ⁇ 0.05%, and the total amount is ⁇ 0.15%;
- the preparation method of the aluminum alloy is the same as that in Example 1, and the aluminum alloy is obtained.
- the extruded products obtained by extrusion treatment and the cold drawn products obtained by cold drawing in the preparation process of the aluminum alloys obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were observed respectively.
- the dimensions of the extruded products are shown in Figure 6.
- the pressed product is a square shell with a wall thickness of 0.50-0.65mm and a circumscribed circle diameter of 128mm; the size of the cold-drawn product obtained by cold drawing is shown in Figure 7. It is a 128mm square shell; according to GB T 228.1-2010 Tensile Test of Metal Materials Part 1 Room Temperature Test Method, use a universal material testing machine to test the tensile strength of the aluminum alloys obtained in Examples 1-3 and Comparative Examples 1-5 , and the test results are shown in Table 1.
- the aluminum alloy for the thin-walled square shell provided by the present invention has good extrusion performance and cold drawing performance; the tensile strength can reach 182-200 MPa, and the tensile strength is high.
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Abstract
本发明属于合金技术领域,特别涉及一种铝合金及其制备方法和应用。本发明提供的铝合金,以质量百分含量计,包括以下元素:Cu 0.10~0.18%、Fe 0.33~0.38%、Mn 1.05~1.10%、Si 0.06~0.18%、Mg 0.10~0.20%、Zr 0.04~0.07%、Cr 0.03~0.05%、Ti≤0.03%、余量的Al和不可避免的杂质;Mn与Fe的质量比为(2.8~3.2):1,Mn与Fe的总含量≤1.45wt.%。实施例表明,本发明提供的铝合金的抗拉强度为182~200MPa;挤压后或冷拔后所得产品表面光滑,挤压性能和冷拔性能优良,适用于薄壁方形壳体型材。
Description
本申请要求于2020年12月17日提交中国专利局、申请号为202011493550.3、发明名称为“一种铝合金及其制备方法和应用”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本发明属于合金技术领域,特别涉及一种铝合金及其制备方法和应用。
动力电池外壳需要具有抗腐蚀性能优良、耐中低温、导热快、焊接性能好且强度中等或较高的性能,目前动力电池外壳通常采用铝拉拔方管或拉伸成型铝桶。在铝合金中,由于1000系铝合金强度太低,因此虽然具有纯度高、易挤压的优点,但无法满足动力电池外壳的基本强度需求;3000系铝合金属于不可热处理强化的铝合金,只能采用冷加工处理方法提高强度,当冷加工变形量较大时,容易出现拉断问题,量产性能低,如对于方形壳体,当变形量大于35%时,容易出现拉断情况,尤其是方形壳体角部位置容易出现拉断、破碎现象。目前的铝合金无法在保证良好强度和拉拔性能的基础上实现薄壁方形壳体的生产,也就无法满足动力电池外壳的生产和使用需求。
发明内容
有鉴于此,本发明的目的在于提供一种铝合金及其制备方法,本发明提供的铝合金具有挤压性能优良、冷拔性能优良且抗拉强度高的特点,可以满足薄壁方形壳体型材对强度和挤压、冷拔性能的需求。
为了实现上述发明的目的,本发明提供以下技术方案:
本发明提供了一种铝合金,以质量百分含量计,包括以下元素:
Cu 0.10~0.18%、Fe 0.33~0.38%、Mn 1.05~1.10%、Si 0.06~0.18%、Mg 0.10~0.20%、Zr 0.04~0.07%、Cr 0.03~0.05%、Ti≤0.03%、余量的Al和不可避免的杂质;
Mn与Fe的质量比为(2.8~3.2):1,Mn与Fe的总含量≤1.45wt.%。
优选的,以质量百分含量计,所述不可避免的杂质中单个元素的含量≤0.05%,不可避免的杂质的总含量≤0.15%。
优选的,所述不可避免的杂质包括V、Ca和Na中的一种或多种。
优选的,所述铝合金的抗拉强度为180~200MPa。
优选的,所述铝合金在挤压条件下:极限壁厚为0.55mm,方形断面型材的极限外接圆直径为140mm;
所述铝合金在拉拔条件下:极限壁厚为0.4mm,方形断面型材的极限外接圆直径为138.5mm。
本发明还提供了上述技术方案所述铝合金的制备方法,包括以下步骤:
将合金原料依次进行熔炼和铸造,得到铝合金铸锭;
将所述铝合金铸锭依次进行均匀化处理、挤压处理、淬火、时效处理和冷拔,得到所述铝合金。
优选的,所述熔炼的温度为740~780℃,时间为2~4h。
优选的,所述铸造的温度为690~740℃。
优选的,所述均匀化处理包括依次进行的第一均匀化处理、第二均匀化处理和第三均匀化处理;
所述第一均匀化处理的保温温度为520~540℃,保温时间为2~4h;
所述第二均匀化处理的保温温度为580~600℃,保温时间为6~10h;
所述第三均匀化处理的保温温度为460~480℃,保温时间为2~4h。
优选的,所述第一均匀化处理的保温温度由室温升温得到,所述升温的速率为2~5℃/min。
优选的,所述第二均匀化处理的保温温度由第一均匀化处理的保温温度升温得到;所述升温的速率为2~5℃/min。
优选的,所述三均匀化处理的保温温度由第二均匀化处理的保温温度降温得到;所述降温的速率为0.5~2℃/min。
优选的,所述挤压处理的温度为460~520℃,挤压比为30~150。
优选的,所述淬火的冷却速率≥100℃/min。
优选的,所述时效处理的保温温度为150~170℃,保温时间为1~3h。
优选的,所述时效处理的保温温度由室温升温得到;所述升温的速率为3~10℃/min。
优选的,所述冷拔为一次冷拔,所述冷拔的变形量为15~30%。
本发明还提供了上述技术方案所述铝合金或上述技术方案所述制备方法制备的铝合金作为薄壁方形壳体型材在电池外壳中的应用。
本发明还提供了一种方形壳体,由上述技术方案所述铝合金或上述技术方案所述制备方法得到的铝合金制备得到,所述制备的方法包括挤压或冷拔;
挤压所得方形壳体的壁厚为0.50~0.65mm;
冷拔所得方形壳体的壁厚为0.40~0.50mm。
本发明提供了一种铝合金,以质量百分含量计,包括以下元素:Cu 0.10~0.18%、Fe 0.33~0.38%、Mn 1.05~1.10%、Si 0.06~0.18%、Mg 0.10~0.20%、Zr 0.04~0.07%、Cr 0.03~0.05%、Ti≤0.03%、余量的Al和不可避免的杂质;Mn与Fe的质量比为(2.8~3.2):1,Mn与Fe的总含量≤1.45wt.%。
在本发明中,Al提供基体合金元素;Mn为主合金元素,Mn与Al形成MnAl
6相,而且Mn的添加有利于Fe相硬质颗粒球化,有利于提高合金的挤压加工性能;Cu有利于提高铝合金的强度;Mg有利于细化铝合金的晶粒度和提高强度;Fe有利于形成(FeMn)Al
6相,可有效细化铝合金晶粒;Al、Si和Mn可以形成三元相Al
12Mn
3Si
2,当三元相Al
12Mn
3Si
2溶解Fe后会形成四元相AlFeMnSi,本发明控制Fe和Si含量保证在形成三元相和四元相基础上,Fe和Si仍可以发挥对铝合金晶粒细化或固溶强化的作用;Cu、Si和Mg均具有固溶强化的作用,Si和Mg可析出Mg
2Si强化相,有利于增强铝合金的强度;Zr、Cr是铝合金的微合金化元素,由Zr、Cr与Al形成的AlCr
7和AlZr
3,是热力学稳定的微细弥散相,有利于抑制铝合金的再结晶和晶粒长大;Ti有利于细化铸造晶粒。
此外,Mn控制在1.05~1.10wt.%,有利于提高铝合金塑性、焊接性、耐热性和耐腐蚀性,同时避免挤压变形抗力大,防止挤压性能的严重恶化;将Si、Mg和Cu控制在相应的含量范围内,有利于保证铝合金的强度,同时避免铝合金挤压变形抗力大,防止挤压性能的恶化,还可以保证形成Mg
2Si强化相,避免Fe的有利影响被削弱;同时控制Zr和Cr的含量,有利于确保铝合金具有纤维晶组织,防止形成粗大再结晶组织和纤维晶组织共存的混合晶粒组织,避免铝合金的强度和挤压性能的恶化;控制Mn和Fe的含量关系,有利于避免形成大量粗大片状(FeMn)Al
6,防止铝合金延展性的降低,还有利于平衡铝合金的强度与挤压性之间的关系,满足薄壁方形壳体对强度和挤压性能的需求。
实施例测试结果表明,本发明提供的铝合金的抗拉强度为182~200MPa;挤压后挤出品表面光滑(挤出品为壁厚为0.5~0.65mm,外接圆直接为128mm的方壳),挤压性能优良;冷拔后冷拔品表面光滑(冷拔品为壁厚为0.4~0.5mm,外接圆直接为128mm的方壳),冷拔性能优良。
本发明还提供了一种铝合金的制备方法,包括以下步骤:将合金原料依次进行熔炼和铸造,得到铝合金铸锭;将所述铝合金铸锭依次进行均匀化处理、挤压处理、淬火、时效处理和冷拔,得到所述铝合金。在本发明中,均匀化处理有利于消除铸锭内部合金元素的宏微观偏析,使合金元素和粗大化合物充分固溶,同时形成细小弥散体;时效处理有助于使铝合金中的强化相(Mg
2Si)析出,提高铝合金的强度。
说明书附图
图1为本发明中铝合金的制备方法流程图;
图2为实施例1中铝合金的金相图;
图3为实施例1中铝合金的EBSD照片;
图4为实施例1中铝合金的SEM图;
图5为实施例1中铝合金的EDS图;
图6为挤压测试中试样的尺寸图;
图7为冷拔测试中试样的尺寸图。
下面结合实施例和附图对本发明进一步说明。
本发明提供了一种铝合金,其特征在于,以质量百分含量计,包括以下元素:
Cu 0.10~0.18%、Fe 0.33~0.38%、Mn 1.05~1.10%、Si 0.06~0.18%、Mg 0.10~0.20%、Zr 0.04~0.07%、Cr 0.03~0.05%、Ti≤0.03%、余量的Al和不可避免的杂质;
Mn与Fe的质量比为(2.8~3.2):1,Mn与Fe的总含量≤1.45wt.%。
以质量百分含量计,本发明所述铝合金包括0.10~0.18%的Cu,优选为0.11~0.17%,更优选为0.12~0.16%。在本发明中,Cu具有固溶强化的作用,有利于提高铝合金的强度;Cu控制在含量范围内,有利于保证铝合金的强度,同时避免铝合金挤压变形抗力大,防止挤压性能的恶化。
以质量百分含量计,本发明所述铝合金包括0.33~0.38%的Fe,优选为0.335~0.375%,更优选为0.34~0.37%。在本发明中,Fe有利于形成(FeMn)Al
6相,可有效细化铝合金晶粒。
以质量百分含量计,本发明所述铝合金包括1.05~1.10%的Mn,优选为1.055~1.095%,更优选为1.06~1.09%。在本发明中,Mn为主合金元素,Mn与Al形成MnAl
6相,而且Mn的添加有利于Fe相硬质颗粒球化,有利于提高合金的挤压加工性能;将Mn控制在1.05~1.10wt.%,有利于提高铝合金塑性、焊接性、耐热性和耐腐蚀性,同时避免挤压变形抗力大,防止挤压性能的严重恶化。
以质量百分含量计,本发明所述铝合金包括0.06~0.18%的Si,优选为0.07~0.17%,更优选为0.08~0.16%。在本发明中,Si具有固溶强化的作用,Al、Si和Mn可以形成三元相Al
12Mn
3Si
2,当三元相Al
12Mn
3Si
2溶解Fe后会形成四元相AlFeMnSi。
以质量百分含量计,本发明所述铝合金包括0.10~0.20%的Mg,优选为0.11~0.19%,更优选为0.12~0.18%。在本发明中,Mg具有固溶强化的作用,有利于细化铝合金的晶粒度和提高强度;而且,Si和Mg可析出Mg
2Si强化相,有利于增强铝合金的强度;将Si和Mg控制在 相应的含量范围内,有利于保证铝合金的强度,同时避免铝合金挤压变形抗力大,防止挤压性能的恶化,还可以保证形成Mg
2Si强化相,避免削弱Fe的有利影响。
以质量百分含量计,本发明所述铝合金包括0.04~0.07%的Zr,优选为0.045~0.065%,更优选为0.05~0.06%。在本发明中,Zr是铝合金的微合金化元素,由Zr与Al形成的AlZr
3,是热力学稳定的微细弥散相,有利于抑制铝合金的再结晶和晶粒长大;控制Zr的含量,有利于确保铝合金具有纤维晶组织,防止形成粗大再结晶组织和纤维晶组织共存的混合晶粒组织,避免铝合金的强度和挤压性能的恶化。
以质量百分含量计,本发明所述铝合金包括0.03~0.05%的Cr,优选为0.033~0.048%,更优选为0.035~0.045%。在本发明中,Cr是铝合金的微合金化元素,由Cr与Al形成的AlCr
7,是热力学稳定的微细弥散相,有利于抑制铝合金的再结晶和晶粒长大。控制Cr的含量,有利于确保铝合金具有纤维晶组织,防止形成粗大再结晶组织和纤维晶组织共存的混合晶粒组织,避免铝合金的强度和挤压性能的恶化。
以质量百分含量计,本发明所述铝合金包括Ti≤0.03%,优选为0.001~0.028%,更优选为0.01~0.02%。在本发明中,Ti有利于铸造晶粒的细化。
以质量百分含量计,本发明所述铝合金包括余量的Al和不可避免的杂质。
在本发明中,Al为基体合金元素。
在本发明中,以质量百分含量计,所述不可避免的杂质中单个元素的含量优选≤0.05%,更优选≤0.03%,再优选≤0.01%;所述不可避免的杂质的总含量优选≤0.15%,更优选≤0.1%,再优选≤0.05%。在本发明中,所述不可避免的杂质优选包括V、Ca和Na中的一种或多种。
在本发明中,所述Mn与Fe的质量比为(2.8~3.2):1,优选为(2.85~3.15):1,更优选为(2.9~3.1):1;Mn与Fe的总含量优选≤1.45wt.%,更优选≤1.40%。本发明中控制Mn和Fe的含量关系,有 利于避免形成大量粗大片状(FeMn)Al
6,防止铝合金延展性的降低,还有利于平衡铝合金的强度与挤压性之间的关系,满足薄壁方形壳体型材对强度和挤压性能的需求。
在本发明中,所述铝合金的抗拉强度优选为180~200MPa。在本发明中,所述铝合金在挤压条件下:极限壁厚优选为0.55mm,方形断面型材的极限外接圆直径优选为140mm。在本发明中,所述铝合金在拉拔条件下:极限壁厚优选为0.4mm,方形断面型材的极限外接圆直径优选为138.5mm。
本发明还提供了上述技术方案所述铝合金的制备方法,包括以下步骤:
将合金原料依次进行熔炼和铸造,得到铝合金铸锭;
将所述铝合金铸锭依次进行均匀化处理、挤压处理、淬火、时效处理和冷拔,得到所述铝合金。
图1为本发明中铝合金的制备方法流程图,下面结合图1对本发明提供的铝合金的制备方法进行详细说明。
本发明将合金原料依次进行熔炼和铸造,得到铝合金铸锭。
本发明对所述合金原料没有特殊限定,采用任意能够满足所述薄壁方形壳体用铝合金元素组成的合金原料即可。
在本发明中,所述熔炼的温度优选为740~780℃,更优选为750~760℃;熔炼的时间优选为2~4h,更优选为2~3h。在本发明中,所述熔炼的设备优选为倾动式熔化炉。
在本发明中,所述铸造的温度优选为690~740℃,更优选为700~720℃。
得到铝合金铸锭后,本发明将所述铝合金铸锭依次进行均匀化处理、挤压处理、淬火、时效处理和冷拔,得到所述薄壁方形壳体用铝合金。
本发明将所述铝合金铸锭进行均匀化处理,得到均匀化铸锭。
在本发明中,所述均匀化处理优选包括依次进行的第一均匀化处理、第二均匀化处理和第三均匀化处理。在本发明中,所述均匀化处 理有利于消除铸锭内部合金元素的宏微观偏析,使合金元素和粗大化合物充分固溶,同时形成细小弥散体。
在本发明中,所述第一均匀化处理的保温温度优选为520~540℃,更优选为525~535℃;保温时间优选为2~4h,更优选为2.5~3.5h。在本发明中,所述第一均匀化处理的保温温度优选由室温升温得到;所述升温的速率优选为2~5℃/min,更优选为3~4℃/min。在本发明中,所述第一均匀化处理有利于完全消除铸锭内部Si、Mg、Cu元素的宏微观偏析。
在本发明中,所述第二均匀化处理的保温温度优选为580~600℃,更优选为585~595℃;保温时间优选为6~10h,更优选为6.5~9.5h。在本发明中,所述第二均匀化处理的保温温度优选由第一均匀化处理的保温温度升温得到;所述升温的速率优选为2~5℃/min,更优选为3~4℃/min。在本发明中,所述第二均匀化处理有利于促进Fe相球化以及将第一均匀化处理析出的高温析出相重新固溶,为后续第三阶段析出做准备。
在本发明中,所述第三均匀化处理的保温温度优选为460~480℃,更优选为465~475℃;保温时间优选为2~4h,更优选为2.5~3.5h。在本发明中,所述第三均匀化处理的保温温度优选由第二均匀化处理的保温温度降温得到;所述降温的速率优选为0.5~2℃/min,更优选为1~1.5℃/min。在本发明中,所述第三均匀化处理有利于保证高温析出相AlCr
7、AlZr
3、MnAl
6充分而细小地弥散析出。在本发明中,如果均匀化处理的参数不在本发明所述的参数范围内,会导致铝合金变形抗力过大,挤压困难,且后续的挤压处理工序会形成纤维晶和粗大晶粒共存的混合晶状态,极大影响铝合金产品的强度。
第三均匀化处理后,本发明优选将所得的均匀化铸锭冷却至室温;所述冷却优选为空冷。
得到均匀化铸锭后,本发明将所述均匀化铸锭依次进行挤压处理和淬火,得到变形铝合金。
在本发明中,所述挤压处理的温度优选为460~520℃,更优选为465~515℃。在本发明中,所述挤压处理的温度优选由室温升温得到; 本发明对所述升温的速率没有特殊限定,采用任意升温速率均可。在本发明中,所述挤压处理的挤压比优选为30~150,更优选为40~80。在本发明中,所述挤压处理的设备优选为正向单动挤压机。在本发明中,所述挤压处理有利于实现合金强化相固溶,而且挤压处理结合挤压模具可以获得产品雏形,有利于实现精准的工艺控制。
在本发明中,所述淬火优选为在线风冷淬火。在本发明中,所述淬火的冷却速率优选≥100℃/min,更优选为100~120℃/min。在本发明中,所述淬火有利于Mg和Si以过饱和固溶体形式保留在产品中。
得到变形铝合金后,本发明将所述变形铝合金进行时效处理,得到时效铝合金。
在本发明中,所述时效处理的保温温度优选为150~170℃,更优选为155~165℃;保温时间优选为1~3h,更优选为1.5~2.5h。在本发明中,所述时效处理的温度优选由室温升温得到;所述升温的速率优选为3~10℃/min,更优选为7~10℃/min。在本发明中,所述时效处理有助于使铝合金中的强化相(Mg
2Si)析出,提高铝合金的强度;在本发明所述时效处理的条件范围内,有利于同时保证铝合金强度和拉拔能力,防止铝合金强度降低或拉拔困难的发生。
得到时效铝合金后,本发明将所述时效铝合金进行拉拔,得到所述铝合金。
在本发明中,所述冷拔优选为一次冷拔。在本发明中,所述冷拔的变形量优选为15~30%,更优选为18~28%。在本发明中,所述拉拔有利于配合时效处理,协同提高铝合金的强度、挤压性能和拉拔性能;同时有利于保证铝合金的薄壁方形壳体的成型性能。
本发明还提供了上述技术方案所述铝合金或上述技术方案所述制备方法制备的铝合金作为薄壁方形壳体型材在电池外壳中的应用。
在本发明中,所述应用优选为将所述铝合金直接作为型材合金,进行薄壁方形壳体型材的成型,并将成型所得薄壁方形壳体型材作为电池外壳。
为了进一步说明本发明,下面结合实施例对本发明提供的一种铝合金 及其制备方法和应用进行详细地描述,但不能将它们理解为对本发明保护范围的限定。显然,所描述的实施例仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
按质量百分含量计,设计铝合金的元素组成为Cu 0.10%、Fe 0.33%、Mn 1.05%、Si 0.06%、Mg 0.10%、Zr 0.04%、Cr 0.03%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备:将符合设计元素组成的合金原料在750℃下熔炼3h,将所得的熔液在710℃下进行铸造,得到铝合金铸锭;
将所述铝合金铸锭以3.5℃/min的速率升温至530℃,并在530℃下保温3h,然后以3.5℃/min的速率升温至580℃,并在580℃下保温8h,再以1.0℃/min的速率降温至460℃,并在460℃下保温2h,空冷至室温,得到均匀化铸锭;然后将所得的均匀化铸锭加热至480℃后进行挤压,挤压比为50,然后以冷却速率为100℃/min进行在线风冷淬火,得到变形铝合金;将所得的变形铝合金以5℃/min的速率加热至150℃,并在150℃下保温2h进行时效处理,得到时效铝合金;将所得的时效铝合金进行变形量为25%的一次冷拔,得到所述铝合金。
对实施例1所得的铝合金进行金相显微镜观察,所得金相图见图2。对实施例1所得铝合金进行电子背散射衍射测试,所得EBSD照片见图3。由图2~3可见,本发明提供的铝合金晶粒细小,具有纤维晶组织。
对实施例1所得铝合金进行扫描电子显微镜测试,所得SEM图见图4。由图4可见,本发明提供的铝合金中,不可溶初生第二相(图中球化白色颗粒)细小弥散,无可溶第二相MgSi,高温析出相AlCr
7、AlZr
3和MnAl
6均匀弥散分布。
对图4中“谱图1”位点进行X射线能谱分析,所得EDS图见图5。由图5可见,图4的“谱图1”位点主要含有Mn和Al,形成了 MnAl
6析出相。
实施例2
按质量百分含量计,设计铝合金的元素组成为Cu 0.18%、Fe 0.38%、Mn 1.10%、Si 0.18%、Mg 0.20%、Zr 0.07%、Cr 0.05%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备:将符合设计元素组成的合金原料在760℃下熔炼3h,将所得的熔液在710℃下进行铸造,得到铝合金铸锭;
将所述铝合金铸锭以3.5℃/min的速率升温至530℃,并在530℃下保温3h,然后以3.5℃/min的速率升温至580℃,并在580℃下保温8h,再以1.0℃/min的速率降温至460℃,并在460℃下保温2h,空冷至室温,得到均匀化铸锭;然后将所得的均匀化铸锭加热至480℃后进行挤压,挤压比为40,然后以冷却速率为100℃/min进行在线风冷淬火,得到变形铝合金;将所得的变形铝合金以5℃/min的速率加热至150℃,并在150℃下保温2h进行时效处理,得到时效铝合金;将所得的时效铝合金进行变形量为25%的一次冷拔,得到所述铝合金。
实施例3
按质量百分含量计,设计铝合金的元素组成为Cu 0.15%、Fe 0.38%、Mn 1.07%、Si 0.10%、Mg 0.17%、Zr 0.05%、Cr 0.05%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备:将符合设计元素组成的合金原料在750℃下熔炼3h,将所得的熔液在710℃下进行铸造,得到铝合金铸锭;
将所述铝合金铸锭以3℃/min的速率升温至530℃,并在530℃下保温3h,然后以3℃/min的速率升温至580℃,并在580℃下保温8h,再以0.8℃/min的速率降温至460℃,并在460℃下保温2h,空冷至室温,得到均匀化铸锭;然后将所得的均匀化铸锭加热至480℃后进行挤压,挤压比为30,然后以冷却速率为100℃/min进行在线风冷淬火,得到变形铝合金;将所得的变形铝合金以5℃/min的速率加热至 150℃,并在150℃下保温2h进行时效处理,得到时效铝合金;将所得的时效铝合金进行变形量为25%的一次冷拔,得到所述铝合金。
实施例4
按质量百分含量计,设计铝合金的元素组成为Cu 0.12%、Fe 0.34%、Mn 1.05%、Si 0.09%、Mg 0.16%、Zr 0.04%、Cr 0.03%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备:将符合设计元素组成的合金原料在760℃下熔炼4h,将所得的熔液在720℃下进行铸造,得到铝合金铸锭;
将所述铝合金铸锭以3.5℃/min的速率升温至530℃,并在530℃下保温3h,然后以3.5℃/min的速率升温至580℃,并在580℃下保温8h,再以1.0℃/min的速率降温至460℃,并在460℃下保温2h,空冷至室温,得到均匀化铸锭;然后将所得的均匀化铸锭加热至480℃后进行挤压,挤压比为50,然后以冷却速率为100℃/min进行在线风冷淬火,得到变形铝合金;将所得的变形铝合金以5℃/min的速率加热至150℃,并在150℃下保温2h进行时效处理,得到时效铝合金;将所得的时效铝合金进行变形量为25%的一次冷拔,得到所述铝合金。
对比例1
按质量百分含量计,设计铝合金的元素组成为Cu 0.15%、Fe 0.30%、Mn 1.06%、Si 0.10%、Mg 0.17%、Zr 0.02%、Cr 0.02%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备方法与实施例1一致,得到铝合金。
对比例2
按质量百分含量计,设计铝合金的元素组成为Cu 0.15%、Fe 0.38%、Mn 1.07%、Si 0.10%、Mg 0.17%、Zr 0.05%、Cr 0.05%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备方法中,均匀处理为:将铝合金铸锭以3℃/min的速 率升温至530℃,并在530℃下保温3h,然后以3℃/min的速率升温至580℃,并在580℃下保温8h,空冷至室温,得到均匀化铸锭;其余技术手段与实施例3一致,得到铝合金。
对比例3
按质量百分含量计,设计铝合金的元素组成为Cu 0.15%、Fe 0.38%、Mn 1.07%、Si 0.10%、Mg 0.17%、Zr 0.05%、Cr 0.05%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备方法中,无时效处理,其余技术手段与实施例3一致,得到铝合金。
对比例4
按质量百分含量计,设计铝合金的元素组成为Cu 0.15%、Fe 0.38%、Mn 1.07%、Si 0.10%、Mg 0.17%、Zr 0.05%、Cr 0.05%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备方法中,均匀处理为:将铝合金铸锭以3℃/min的速率升温至530℃,并在530℃下保温3h,然后以3℃/min的速率升温至560℃,并在560℃下保温8h,再以0.8℃/min的速率降温至460℃,并在460℃下保温2h,空冷至室温,得到均匀化铸锭;其余技术手段与实施例3一致,得到铝合金。
对比例5
按质量百分含量计,设计铝合金的元素组成为Cu 0.10%、Fe 0.33%、Mn 1.05%、Si 0.06%、Mg 0.10%、Cr 0.10%、Ti 0.02%、余量的Al和不可避免的杂质;不可避免的杂质中单个含量≤0.05%,总量≤0.15%;
铝合金的制备方法与实施例1一致,得到铝合金。
对实施例1~3和对比例1~5所得铝合金制备过程中挤压处理所得挤压品和冷拔所得冷拔品分别进行观察,其中,挤压品尺寸见图6,挤压所得挤压品为壁厚为0.50~0.65mm、外接圆直径为128mm的方形壳体;冷拔所得冷拔品尺寸见图7,冷拔所得冷拔品为壁厚为0.40~0.50mm、外接 圆直径为128mm的方形壳体;按照GB T 228.1-2010金属材料拉伸试验第1部分室温试验方法,使用万能材料试验机对实施例1~3和对比例1~5所得铝合金进行抗拉强度测试,测试结果见表1。
表1实施例1~3和对比例1~5所得铝合金性能测试结果
注:表1中“/”表示:冷拔为挤压的后工序,因为对比例4未能挤出,因此不能进行冷拔及后续的抗拉强度测试。
由表1可见,本发明提供的薄壁方形壳体用铝合金具有良好的挤压性能和冷拔性能;抗拉强度可达到182~200MPa,抗拉强度高。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (19)
- 一种铝合金,其特征在于,以质量百分含量计,包括以下元素:Cu 0.10~0.18%、Fe 0.33~0.38%、Mn 1.05~1.10%、Si 0.06~0.18%、Mg 0.10~0.20%、Zr 0.04~0.07%、Cr 0.03~0.05%、Ti≤0.03%、余量的Al和不可避免的杂质;Mn与Fe的质量比为(2.8~3.2):1,Mn与Fe的总含量≤1.45wt.%。
- 根据权利要求1所述的铝合金,其特征在于,以质量百分含量计,所述不可避免的杂质中单个元素的含量≤0.05%,不可避免的杂质的总含量≤0.15%。
- 根据权利要求1或2所述的铝合金,其特征在于,所述不可避免的杂质包括V、Ca和Na中的一种或多种。
- 根据权利要求1或2所述的铝合金,其特征在于,所述铝合金的抗拉强度为180~200MPa。
- 根据权利要求1或2所述的铝合金,其特征在于,所述铝合金在挤压条件下:极限壁厚为0.55mm,方形断面型材的极限外接圆直径为140mm;所述铝合金在拉拔条件下:极限壁厚为0.4mm,方形断面型材的极限外接圆直径为138.5mm。
- 权利要求1~5任一项所述铝合金的制备方法,其特征在于,包括以下步骤:将合金原料依次进行熔炼和铸造,得到铝合金铸锭;将所述铝合金铸锭依次进行均匀化处理、挤压处理、淬火、时效处理和冷拔,得到所述铝合金。
- 根据权利要求6所述的制备方法,其特征在于,所述熔炼的温度为740~780℃,时间为2~4h。
- 根据权利要求6所述的制备方法,其特征在于,所述铸造的温度为690~740℃。
- 根据权利要求6所述的制备方法,其特征在于,所述均匀化处理包括依次进行的第一均匀化处理、第二均匀化处理和第三均匀化处 理;所述第一均匀化处理的保温温度为520~540℃,保温时间为2~4h;所述第二均匀化处理的保温温度为580~600℃,保温时间为6~10h;所述第三均匀化处理的保温温度为460~480℃,保温时间为2~4h。
- 根据权利要求9所述的制备方法,其特征在于,所述第一均匀化处理的保温温度由室温升温得到,所述升温的速率为2~5℃/min。
- 根据权利要求9所述的制备方法,其特征在于,所述第二均匀化处理的保温温度由第一均匀化处理的保温温度升温得到;所述升温的速率为2~5℃/min。
- 根据权利要求9所述的制备方法,其特征在于,所述三均匀化处理的保温温度由第二均匀化处理的保温温度降温得到;所述降温的速率为0.5~2℃/min。
- 根据权利要求6所述的制备方法,其特征在于,所述挤压处理的温度为460~520℃,挤压比为30~150。
- 根据权利要求6所述的制备方法,其特征在于,所述淬火的冷却速率≥100℃/min。
- 根据权利要求6所述的制备方法,其特征在于,所述时效处理的保温温度为150~170℃,保温时间为1~3h。
- 根据权利要求6或15所述的制备方法,其特征在于,所述时效处理的保温温度由室温升温得到;所述升温的速率为3~10℃/min。
- 根据权利要求6所述的制备方法,其特征在于,所述冷拔为一次冷拔,所述冷拔的变形量为15~30%。
- 权利要求1~5任一项所述铝合金或权利要求6~17任一项所述制备方法制备的铝合金作为薄壁方形壳体型材在电池外壳中的应用。
- 一种方形壳体,由权利要求1~5任一项所述铝合金或权利要求6~17任一项所述制备方法得到的铝合金制备得到,所述制备的方法包括挤压或冷拔;挤压所得方形壳体的壁厚为0.50~0.65mm;冷拔所得方形壳体的壁厚为0.40~0.50mm。
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