US20190390305A1 - Semi-solid die-casting aluminum alloy and method for preparing semi-solid die-casting aluminum alloy casting - Google Patents
Semi-solid die-casting aluminum alloy and method for preparing semi-solid die-casting aluminum alloy casting Download PDFInfo
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- US20190390305A1 US20190390305A1 US16/465,321 US201716465321A US2019390305A1 US 20190390305 A1 US20190390305 A1 US 20190390305A1 US 201716465321 A US201716465321 A US 201716465321A US 2019390305 A1 US2019390305 A1 US 2019390305A1
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 181
- 238000004512 die casting Methods 0.000 title claims abstract description 135
- 239000007787 solid Substances 0.000 title claims abstract description 120
- 238000005266 casting Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 238000005275 alloying Methods 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 64
- 239000000956 alloy Substances 0.000 claims description 64
- 239000010949 copper Substances 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 11
- 229910018131 Al-Mn Inorganic materials 0.000 claims description 9
- 229910018182 Al—Cu Inorganic materials 0.000 claims description 9
- 229910018461 Al—Mn Inorganic materials 0.000 claims description 9
- 229910018575 Al—Ti Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910000676 Si alloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910021364 Al-Si alloy Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 42
- 238000007670 refining Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 229910018125 Al-Si Inorganic materials 0.000 description 6
- 229910018520 Al—Si Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- -1 aluminum-silicon-copper Chemical compound 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MIOQWPPQVGUZFD-UHFFFAOYSA-N magnesium yttrium Chemical compound [Mg].[Y] MIOQWPPQVGUZFD-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910009929 Ti2Cu3 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- AVXOKCVGOCIRCC-UHFFFAOYSA-N [Ce].[La].[Mg] Chemical compound [Ce].[La].[Mg] AVXOKCVGOCIRCC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/007—Semi-solid pressure die casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Definitions
- the present disclosure relates to the field of alloys and, in particular, to a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting.
- Die casting is a liquid molding method. Due to the high injection speed, the liquid easily forms turbulent flow in the mold cavity, and the air in the mold cavity is drawn into the product. When the liquid hits the mold, the temperature difference is large, the liquid on the surface is rapidly solidified, which increases the flow resistance of the core liquid, so it cannot be well fused to form a cold partition. Due to the introduction of oxides or some other impurities in the alloy smelting and casting process, the product performance is ultimately lowered.
- die-casting aluminum alloys have been rapidly applied.
- the 1980s 68% of aluminum alloy components in the United States were produced by die-casting technology.
- the die-casting aluminum alloys used in the industry mainly include aluminum-silicon alloys, aluminum-magnesium alloys, aluminum-zinc alloys, aluminum-silicon-copper alloys, and aluminum-silicon-magnesium alloys.
- the most commonly used die-casting alloy for die casting is ADC12, which has a yield strength of about 190 MPa, a tensile strength of about 280 MPa, and an elongation of 2 to 3%, and cannot be strengthened by heat treatment.
- the wrought aluminum alloy (including aluminum alloy for extrusion, forging, rolling, etc.) has high mechanical properties and stable performance, but due to the harsh process conditions and high equipment requirements, it is impossible to form complicated parts, and it is impossible to realize the demands of simplification and integration for automobile parts.
- An objective of the present disclosure is to provide a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting.
- the semi-solid die-casting aluminum alloy has high strength and high plasticity, can be subjected to high pressure casting, and can form various complicated parts and ensure high mechanical properties.
- the present disclosure provides a semi-solid die-casting aluminum alloy, containing alloying elements, inevitable impurities and the balance of an aluminum element; based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti and 0.01 to 0.35 wt % of rare earth element.
- the alloying elements include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element.
- the rare earth element includes at least one of La, Ce, Pr and Nd.
- the impurities in the semi-solid die-casting aluminum alloy are not more than 0.8 wt %.
- the ratio of the weight content of Ti to Cu is 1:(14 to 90).
- the semi-solid die-casting aluminum alloy includes 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % Ti, 0.01 to 0.35 wt % of rare earth element, no more than 0.8 wt % of impurities and the balance of aluminum.
- the semi-solid die-casting aluminum alloy includes 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % Ti, 0.15 to 0.25 wt % of rare earth element, no more than 0.7 wt % of impurities and the balance of aluminum.
- the semi-solid die-casting aluminum alloy has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
- the semi-solid die-casting aluminum alloy has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
- the present disclosure further provides a method for preparing a semi-solid die-casting aluminum alloy casting, including: after performing ratio smelting on aluminum alloy raw materials, performing semi-solid die casting to obtain the semi-solid die-casting aluminum alloy casting; where the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti, 0.01 to 0.35 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti, 0.15 to 0.25 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- the aluminum alloy raw materials are elemental metals or metal alloys.
- the aluminum alloy raw materials are elemental aluminum or an alloy of aluminum, elemental silicon or an alloy of silicon, elemental copper or an alloy of copper, elemental manganese or an alloy of manganese, elemental titanium or an alloy of titanium, and an elemental rare earth element or an alloy containing a rare earth element.
- the aluminum alloy raw materials are elemental aluminum, an Al—Si alloy, an Al—Ti alloy, an Al—Cu alloy, an Al—Mn alloy and an Al—Re intermediate alloy.
- the purity of the elemental metal is 99.9 wt % or more, and the total content of the alloying elements in the metal alloy is 99.9 wt % or more.
- the adjustment and optimization of the formula and the addition of rare earth elements have the purification effect of removing gases and impurities and the modification effect of refining crystal grains on the alloy melt, and also increase the melt fluidity and enhance the casting properties.
- the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure adopts the above semi-solid die-casting aluminum alloy for semi-solid die casting.
- the method can form various complicated components, enhances the mechanical properties of the casting, reduces the defects of the casting, and enhances the yield.
- the present disclosure provides a semi-solid die-casting aluminum alloy, containing alloying elements, inevitable impurities and the balance of an aluminum element; based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti and 0.01 to 0.35 wt % of rare earth element.
- the adjustment and optimization of the formula and the addition of rare earth elements have the purification effect of removing gases and impurities and the modification effect of refining crystal grains on the alloy melt, and also increase the melt fluidity and enhance the casting properties.
- the semi-solid die-casting aluminum alloy of the present disclosure when the composition of the semi-solid die-casting aluminum alloy is within the above range, high mechanical properties can be obtained while good casting properties are obtained.
- the semi-solid die-casting aluminum alloy obtained by using the formula has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
- the alloying elements include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element.
- the semi-solid die-casting aluminum alloy obtained according to the formula has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
- the kind of the rare earth element is not particularly limited, may be a conventional kind well known to those skilled in the art, and may be a single kind of rare earth element or mixed rare earths.
- the rare earth element may include at least one of La, Ce, Pr and Nd, and the relative content of each rare earth element is also not particularly required.
- the above rare earth element may be a commercially available product and is industrial mixed rare earths.
- the purity of the semi-solid die-casting aluminum alloy is one of the important factors affecting the performance of the aluminum alloy.
- the impurities in the semi-solid die-casting aluminum alloy are not more than 0.8 wt %.
- the addition of the metal element titanium in the semi-solid die-casting aluminum alloy can refine the crystal grains, enhance the strength and plasticity of the alloy, improve the fluidity of the alloy and enhance the casting properties.
- the added metal element copper can form a Ti 2 Cu 3 phase with titanium and be distributed at the grain boundary, so that the grain boundary slip during alloy stretching is effectively suppressed, thereby enhancing the strength of the alloy.
- the ratio of the weight content of Ti to Cu may be 1:(7 to 350), preferably 1:(14 to 90).
- the semi-solid die-casting aluminum alloy may include 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % Ti, 0.01 to 0.35 wt % of rare earth element, no more than 0.8 wt % of impurities and the balance of aluminum.
- the semi-solid die-casting aluminum alloy may include 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % Ti, 0.15 to 0.25 wt % of rare earth element, no more than 0.7 wt % of impurities and the balance of aluminum.
- the present disclosure further provides a method for preparing a semi-solid die-casting aluminum alloy casting, including: after performing ratio smelting on aluminum alloy raw materials, performing semi-solid die casting to obtain the semi-solid die-casting aluminum alloy casting, where the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the aluminum alloy casting, 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti, 0.01 to 0.35 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti, 0.15 to 0.25 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- the melting may be performed in a smelting furnace, and the aluminum alloy raw materials added to the smelting furnace may be simple substances or metal alloys, as long as the composition of the aluminum alloy obtained by smelting the added aluminum alloy raw materials is within the above range.
- the aluminum alloy raw materials may be elemental aluminum or an alloy of aluminum, elemental silicon or an alloy of silicon, elemental copper or an alloy of copper, elemental manganese or an alloy of manganese, elemental titanium or an alloy of titanium, and an elemental rare earth element or an alloy containing a rare earth.
- the above aluminum alloy raw materials are elemental aluminum, an Al—Si alloy, an Al—Ti alloy, an Al—Cu alloy, an Al—Mn alloy and an Al—Re intermediate alloy. Further, to prevent the introduction of impurities from affecting the performance of the aluminum alloy, the purity of the elemental metal is 99.9 wt % or more, and the total content of the alloying elements in the alloy is 99.9 wt % or more.
- the semi-solid die-casting aluminum alloy casting is obtained by performing semi-solid die casting after performing ratio smelting on the aluminum alloy raw materials.
- the smelting and semi-solid die casting can employ conventional methods and operating conditions, and the present disclosure does not impose any particular requirements.
- the smelting process may adopt the existing steps of material preparation ⁇ melting ⁇ refining ⁇ slag removing ⁇ casting.
- the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure may include the following steps:
- Step 1 Material preparation: 1) raw materials: a pure aluminum ingot (purity ⁇ 99.9 wt %), an Al—Si intermediate alloy, an Al—Ti intermediate alloy, an Al—Cu intermediate alloy, an Al—Mn intermediate alloy and an Al—Re intermediate alloy; and 2) fluxes: a covering agent, a refining agent and a modifier, which may be the existing covering agent, refining agent and modifier for aluminum alloy preparation, for example, the covering agent SY-LF1, the refining agent hexachloroethane and the modifier K2ZrF6.
- a covering agent, a refining agent and a modifier which may be the existing covering agent, refining agent and modifier for aluminum alloy preparation, for example, the covering agent SY-LF1, the refining agent hexachloroethane and the modifier K2ZrF6.
- Step 2 Drying: the prepared raw materials are dried, where the pure aluminum ingot is dried at a temperature of 100° C. ⁇ 10° C., the Al—Si intermediate alloy, the Al—Ti intermediate alloy, the Al—Cu intermediate alloy, the Al—Mn intermediate alloy and the Al—Re intermediate alloy are dried at a temperature of 150° C. ⁇ 10° C., and the purpose of drying is to remove moisture from the raw materials.
- Step 3 Melt alloying: the inner wall of a crucible is coated with the prepared covering agent, the crucible is preheated to 200 to 250° C., the weighed aluminum ingot, Al—Si intermediate alloy, Al—Ti intermediate alloy, Al—Cu intermediate alloy, Al—Mn intermediate alloy and Al—Re intermediate alloy ingot are placed into the crucible, and heated and melted after the addition of the covering agent, and the alloys are stirred uniformly after fully melted, where the time of the entire melting process is controlled within 2 to 3 h, and the final temperature of the aluminum alloy melt is controlled at 750 to 770° C.
- Step 4 Refining: the purpose of refining is to remove non-metallic inclusions in the alloy liquid; at 700 to 720° C., a bell jar is used to press the refining agent hexachloroethane into about 2 ⁇ 3 below the surface of the melt in batches, and is rotated clockwise uniformly and slowly, and when the hexachloroethane is fully reacted, the inclusions and gases in the melt are taken out. The speed of stirring is low.
- the amount of hexachloroethane is related to the alloy composition and the mass of the original ingot, and is generally 0.5 wt % to 0.7 wt % of the charge. Melting is performed in a resistance furnace, and the refining time is within 10 min.
- Step 5 Slag removing: after fully refining with the hexachloroethane, the bell jar is taken out, the residual oxides are removed, and the inclusions on the surface of the melt are removed with a slag spoon.
- Step 6 Casting: after the alloy slag is removed, pouring should be immediately performed after 4 to 10 min of heat preservation to obtain an alloy ingot for die casting or a die-cast block.
- the pouring temperature is generally required to be 720 to 750° C.
- Step 7 Die Casting: the above-mentioned alloy ingot for die casting or die-cast block is die-cast into a sample by a conventional semi-solid die casting process, thereby obtaining the aluminum alloy casting of the present disclosure.
- the aluminum alloy and a method for preparing the same of the present disclosure are further described below by way of embodiments. However, the present disclosure is not limited to the embodiments listed below.
- the rare earth element is mixed rare earths (containing 39.8 wt % of La and 58.8 wt % of Ce).
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 8.5 wt % of Si, 4.0 wt % of Cu, 0.55 wt % of Mn, 0.15 wt % of Ti, 0.20 wt % of rare earth element, and the balance of aluminum.
- the aluminum ingot, the Al—Si intermediate alloy, the Al—Ti intermediate alloy, the Al—Cu intermediate alloy, the Al—Mn intermediate alloy and the Al—Re intermediate alloy ingot measured according to the above semi-solid die-casting aluminum alloy composition were placed into a crucible coated with a covering agent and preheated to 220° C., and were heated and melted after the addition of the covering agent, and the alloys were stirred uniformly after fully melted, where the melting process was 2.5 h, and the final temperature of the aluminum alloy melt was 750° C.; at 700 to 720° C., a bell jar was used to press the refining agent hexachloroethane into about 2 ⁇ 3 below the surface of the melt in batches, and was rotated clockwise uniformly and slowly, for refining for 8 min where the amount of hexachloroethane was 0.5 wt % of the charge; after fully refining, the bell jar was taken out, the residual oxides were removed, and the inclusions on the surface
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- Embodiment 1 The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.5 wt % of Si, 3.5 wt % of Cu, 0.5 wt % of Mn, 0.01 wt % of Ti, 0.01 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A2 of this embodiment.
- the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.5 wt % of Si, 3.5 wt % of Cu, 0.5 wt % of Mn, 0.01 wt % of Ti, 0.01 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A2 of this embodiment.
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- Embodiment 1 The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 7.5 wt % of Si, 4.8 wt % of Cu, 0.75 wt % of Mn, 0.5 wt % of Ti, 0.35 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A3 of this embodiment.
- the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 7.5 wt % of Si, 4.8 wt % of Cu, 0.75 wt % of Mn, 0.5 wt % of Ti, 0.35 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A3 of this embodiment.
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- Embodiment 1 The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.0 wt % of Si, 4.4 wt % of Cu, 0.52 wt % of Mn, 0.10 wt % of Ti, 0.15 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A4 of this embodiment.
- the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.0 wt % of Si, 4.4 wt % of Cu, 0.52 wt % of Mn, 0.10 wt % of Ti, 0.15 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A4 of this embodiment.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that no rare earth element was added, thereby obtaining the aluminum alloy casting B1 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that the content of the rare earth element in the semi-solid die-casting aluminum alloy was 0.5 wt %, thereby obtaining the aluminum alloy casting B2 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing the aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that the content of the Si in the semi-solid die-casting aluminum alloy was 10 wt %, thereby obtaining the aluminum alloy casting B3 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that the content of the Si in the semi-solid die-casting aluminum alloy was 7 wt %, thereby obtaining the aluminum alloy casting B4 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing the aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that the content of the Cu in the semi-solid die-casting aluminum alloy was 5 wt %, thereby obtaining the aluminum alloy casting B5 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method and the raw materials of Embodiment 1 were employed except that the content of the Cu in the semi-solid die-casting aluminum alloy was 3 wt %, thereby obtaining the aluminum alloy casting B6 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method of Embodiment 1 was employed except that a commercially available ADC12 aluminum alloy ingot was used as the ingot, thereby obtaining the aluminum alloy sample B7.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The method of Embodiment 1 was employed except that a commercially available A356.2 aluminum alloy ingot was used as the ingot, thereby obtaining the aluminum alloy sample B8.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Embodiment 1 The raw materials of Embodiment 1 were employed except that a conventional die casting method was used, thereby obtaining the aluminum alloy sample B9.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Pure aluminum (A00 aluminum), an aluminum-manganese alloy (AlMn10), an aluminum-silicon alloy (AlSi12), an aluminum-iron alloy (AlFe10), an aluminum-copper alloy (Al-50Cu), pure magnesium (99.9), pure zinc (99.95), an aluminum-titanium-carbon-boron alloy, magnesium-lanthanum-cerium (Mg—LaCe) and magnesium-yttrium (Mg—Y) were subjected to mixture calculation, smelting and pouring.
- AlMn10 aluminum-manganese alloy
- AlSi12 aluminum-silicon alloy
- AlFe10 aluminum-iron alloy
- Al-50Cu aluminum-copper alloy
- pure magnesium 99.9
- pure zinc 99.95
- an aluminum-titanium-carbon-boron alloy magnesium-lanthanum-cerium (Mg—LaCe) and magnesium-yttrium (Mg—Y) were subjected to mixture calculation, smelting and pouring.
- the contents of the main elements of the finally obtained alloy were as follows: Si: 6.0 wt %, Cu: 0.5 wt %, Fe: 0.42 wt %, Mn: 0.05 wt %, Mg: 1.0 wt %, Zn: 1.5 wt %, Ti: 0.05 wt %, C: 0.002 wt %, LaCe: 0.20 wt %, Y: 0.12 wt %, and the balance of Al and inevitable impurities.
- a conventional die casting method was employed to obtain the aluminum alloy sample B10.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- a pure magnesium ingot and intermediate alloys Al—Si, Al—Mn, Al—Cu, Al—Ti were preheated to 180 to 240° C., the temperature was kept within the range of 740 to 760° C. after pure aluminum was melted, the pure magnesium ingot and the intermediate alloys Al—Si, Al—Mn, Al—Cu, Al—Ti were sequentially added into the aluminum liquid, and after being melted, they were kept at 740° C.
- the alloy liquid was cooled to 750° C. and refined for 15 minutes, the alloy liquid was cooled to 710° C. and subjected to slag removal, then the alloy liquid was cooled to 690° C. and subjected to gas removal, finally the alloy liquid after slag removal and gas removal was cooled to at 680° C. and subjected to die casting, and the heat treatment process was performed after the casting was formed.
- the casting was subjected to solution treatment at a temperature of higher than 545° C. for 3 hours, and then subjected to aging treatment at a temperature of 165° C. for 6 to 12 hours, thereby obtaining the aluminum alloy sample B11.
- the semi-solid die-casting aluminum alloy of the present disclosure has good mechanical properties and casting properties, and the semi-solid die-casting aluminum alloy has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
- the optional alloying elements in the present disclosure include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element, the semi-solid die-casting aluminum alloy obtained according to the formula has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
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Abstract
The present disclosure provides a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting. The semi-solid die-casting aluminum alloy contains alloying elements, inevitable impurities and the balance of aluminum element. Based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti and 0.01 to 0.35 wt % of rare earth element.
Description
- This application claims the priority of Chinese Patent Application No. CN 201611096735.4 filed in China on Dec. 2, 2016, the entire content of which is hereby incorporated by reference.
- The present disclosure relates to the field of alloys and, in particular, to a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting.
- Die casting is a liquid molding method. Due to the high injection speed, the liquid easily forms turbulent flow in the mold cavity, and the air in the mold cavity is drawn into the product. When the liquid hits the mold, the temperature difference is large, the liquid on the surface is rapidly solidified, which increases the flow resistance of the core liquid, so it cannot be well fused to form a cold partition. Due to the introduction of oxides or some other impurities in the alloy smelting and casting process, the product performance is ultimately lowered.
- With the rapid development of 3C (Computer, communication, and consumer electronics) and automotive products, die-casting aluminum alloys have been rapidly applied. By the 1980s, 68% of aluminum alloy components in the United States were produced by die-casting technology. At present, the die-casting aluminum alloys used in the industry mainly include aluminum-silicon alloys, aluminum-magnesium alloys, aluminum-zinc alloys, aluminum-silicon-copper alloys, and aluminum-silicon-magnesium alloys.
- The most commonly used die-casting alloy for die casting is ADC12, which has a yield strength of about 190 MPa, a tensile strength of about 280 MPa, and an elongation of 2 to 3%, and cannot be strengthened by heat treatment. The wrought aluminum alloy (including aluminum alloy for extrusion, forging, rolling, etc.) has high mechanical properties and stable performance, but due to the harsh process conditions and high equipment requirements, it is impossible to form complicated parts, and it is impossible to realize the demands of simplification and integration for automobile parts.
- An objective of the present disclosure is to provide a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting. The semi-solid die-casting aluminum alloy has high strength and high plasticity, can be subjected to high pressure casting, and can form various complicated parts and ensure high mechanical properties.
- To achieve the above objective, the present disclosure provides a semi-solid die-casting aluminum alloy, containing alloying elements, inevitable impurities and the balance of an aluminum element; based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti and 0.01 to 0.35 wt % of rare earth element.
- Optionally, based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element.
- Optionally, the rare earth element includes at least one of La, Ce, Pr and Nd.
- Optionally, the impurities in the semi-solid die-casting aluminum alloy are not more than 0.8 wt %.
- Optionally, the ratio of the weight content of Ti to Cu is 1:(14 to 90).
- Optionally, the semi-solid die-casting aluminum alloy includes 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % Ti, 0.01 to 0.35 wt % of rare earth element, no more than 0.8 wt % of impurities and the balance of aluminum.
- Optionally, the semi-solid die-casting aluminum alloy includes 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % Ti, 0.15 to 0.25 wt % of rare earth element, no more than 0.7 wt % of impurities and the balance of aluminum.
- Optionally, the semi-solid die-casting aluminum alloy has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
- Optionally, the semi-solid die-casting aluminum alloy has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
- The present disclosure further provides a method for preparing a semi-solid die-casting aluminum alloy casting, including: after performing ratio smelting on aluminum alloy raw materials, performing semi-solid die casting to obtain the semi-solid die-casting aluminum alloy casting; where the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti, 0.01 to 0.35 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- Optionally, the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti, 0.15 to 0.25 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- Optionally, the aluminum alloy raw materials are elemental metals or metal alloys.
- Optionally, the aluminum alloy raw materials are elemental aluminum or an alloy of aluminum, elemental silicon or an alloy of silicon, elemental copper or an alloy of copper, elemental manganese or an alloy of manganese, elemental titanium or an alloy of titanium, and an elemental rare earth element or an alloy containing a rare earth element.
- Optionally, the aluminum alloy raw materials are elemental aluminum, an Al—Si alloy, an Al—Ti alloy, an Al—Cu alloy, an Al—Mn alloy and an Al—Re intermediate alloy.
- Optionally, the purity of the elemental metal is 99.9 wt % or more, and the total content of the alloying elements in the metal alloy is 99.9 wt % or more.
- Through the above technical solutions, according to the semi-solid die-casting aluminum alloy of the present disclosure, the adjustment and optimization of the formula and the addition of rare earth elements have the purification effect of removing gases and impurities and the modification effect of refining crystal grains on the alloy melt, and also increase the melt fluidity and enhance the casting properties. The method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure adopts the above semi-solid die-casting aluminum alloy for semi-solid die casting. The method can form various complicated components, enhances the mechanical properties of the casting, reduces the defects of the casting, and enhances the yield.
- Other features and advantages of the present disclosure will be described in detail in the detailed description which follows.
- Specific implementations of the present disclosure are described in detail below. It should be understood that the specific implementations described herein are merely illustrative of the present disclosure and are not intended to limit the present disclosure.
- The present disclosure provides a semi-solid die-casting aluminum alloy, containing alloying elements, inevitable impurities and the balance of an aluminum element; based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti and 0.01 to 0.35 wt % of rare earth element.
- According to the semi-solid die-casting aluminum alloy of the present disclosure, the adjustment and optimization of the formula and the addition of rare earth elements have the purification effect of removing gases and impurities and the modification effect of refining crystal grains on the alloy melt, and also increase the melt fluidity and enhance the casting properties. According to the semi-solid die-casting aluminum alloy of the present disclosure, when the composition of the semi-solid die-casting aluminum alloy is within the above range, high mechanical properties can be obtained while good casting properties are obtained. The semi-solid die-casting aluminum alloy obtained by using the formula has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
- According to the present disclosure, to further enhance the mechanical properties and casting properties of the semi-solid die-casting aluminum alloy, optionally, based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element. The semi-solid die-casting aluminum alloy obtained according to the formula has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
- According to the present disclosure, the kind of the rare earth element is not particularly limited, may be a conventional kind well known to those skilled in the art, and may be a single kind of rare earth element or mixed rare earths. To reduce the raw material cost, optionally, the rare earth element may include at least one of La, Ce, Pr and Nd, and the relative content of each rare earth element is also not particularly required. The above rare earth element may be a commercially available product and is industrial mixed rare earths.
- According to the present disclosure, the purity of the semi-solid die-casting aluminum alloy is one of the important factors affecting the performance of the aluminum alloy. To make the semi-solid die-casting aluminum alloy of the present disclosure excellent in performance, optionally, the impurities in the semi-solid die-casting aluminum alloy are not more than 0.8 wt %.
- According to the present disclosure, the addition of the metal element titanium in the semi-solid die-casting aluminum alloy can refine the crystal grains, enhance the strength and plasticity of the alloy, improve the fluidity of the alloy and enhance the casting properties. At the same time, the added metal element copper can form a Ti2Cu3 phase with titanium and be distributed at the grain boundary, so that the grain boundary slip during alloy stretching is effectively suppressed, thereby enhancing the strength of the alloy. To further enhance of the effect of enhancing the performance of the semi-solid die-casting aluminum alloy by the above two elements, optionally, the ratio of the weight content of Ti to Cu may be 1:(7 to 350), preferably 1:(14 to 90).
- To further enhance the mechanical properties and casting properties of the semi-solid die-casting aluminum alloy, optionally, the semi-solid die-casting aluminum alloy may include 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % Ti, 0.01 to 0.35 wt % of rare earth element, no more than 0.8 wt % of impurities and the balance of aluminum.
- Optionally, the semi-solid die-casting aluminum alloy may include 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % Ti, 0.15 to 0.25 wt % of rare earth element, no more than 0.7 wt % of impurities and the balance of aluminum.
- The present disclosure further provides a method for preparing a semi-solid die-casting aluminum alloy casting, including: after performing ratio smelting on aluminum alloy raw materials, performing semi-solid die casting to obtain the semi-solid die-casting aluminum alloy casting, where the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the aluminum alloy casting, 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti, 0.01 to 0.35 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- According to the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure, to obtain a semi-solid die-casting aluminum alloy casting having higher mechanical properties, in an optional case, the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting includes: based on the total weight of the semi-solid die-casting aluminum alloy casting, 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti, 0.15 to 0.25 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
- According to the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure, the melting may be performed in a smelting furnace, and the aluminum alloy raw materials added to the smelting furnace may be simple substances or metal alloys, as long as the composition of the aluminum alloy obtained by smelting the added aluminum alloy raw materials is within the above range. In an optional case, the aluminum alloy raw materials may be elemental aluminum or an alloy of aluminum, elemental silicon or an alloy of silicon, elemental copper or an alloy of copper, elemental manganese or an alloy of manganese, elemental titanium or an alloy of titanium, and an elemental rare earth element or an alloy containing a rare earth. In an optional case, the above aluminum alloy raw materials are elemental aluminum, an Al—Si alloy, an Al—Ti alloy, an Al—Cu alloy, an Al—Mn alloy and an Al—Re intermediate alloy. Further, to prevent the introduction of impurities from affecting the performance of the aluminum alloy, the purity of the elemental metal is 99.9 wt % or more, and the total content of the alloying elements in the alloy is 99.9 wt % or more.
- According to the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure, the semi-solid die-casting aluminum alloy casting is obtained by performing semi-solid die casting after performing ratio smelting on the aluminum alloy raw materials. The smelting and semi-solid die casting can employ conventional methods and operating conditions, and the present disclosure does not impose any particular requirements.
- For example, the smelting process may adopt the existing steps of material preparation→melting→refining→slag removing→casting. Specifically, the method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure may include the following steps:
- Step 1: Material preparation: 1) raw materials: a pure aluminum ingot (purity≥99.9 wt %), an Al—Si intermediate alloy, an Al—Ti intermediate alloy, an Al—Cu intermediate alloy, an Al—Mn intermediate alloy and an Al—Re intermediate alloy; and 2) fluxes: a covering agent, a refining agent and a modifier, which may be the existing covering agent, refining agent and modifier for aluminum alloy preparation, for example, the covering agent SY-LF1, the refining agent hexachloroethane and the modifier K2ZrF6.
- Step 2: Drying: the prepared raw materials are dried, where the pure aluminum ingot is dried at a temperature of 100° C.±10° C., the Al—Si intermediate alloy, the Al—Ti intermediate alloy, the Al—Cu intermediate alloy, the Al—Mn intermediate alloy and the Al—Re intermediate alloy are dried at a temperature of 150° C.±10° C., and the purpose of drying is to remove moisture from the raw materials.
- Step 3: Melt alloying: the inner wall of a crucible is coated with the prepared covering agent, the crucible is preheated to 200 to 250° C., the weighed aluminum ingot, Al—Si intermediate alloy, Al—Ti intermediate alloy, Al—Cu intermediate alloy, Al—Mn intermediate alloy and Al—Re intermediate alloy ingot are placed into the crucible, and heated and melted after the addition of the covering agent, and the alloys are stirred uniformly after fully melted, where the time of the entire melting process is controlled within 2 to 3 h, and the final temperature of the aluminum alloy melt is controlled at 750 to 770° C.
- Step 4: Refining: the purpose of refining is to remove non-metallic inclusions in the alloy liquid; at 700 to 720° C., a bell jar is used to press the refining agent hexachloroethane into about ⅔ below the surface of the melt in batches, and is rotated clockwise uniformly and slowly, and when the hexachloroethane is fully reacted, the inclusions and gases in the melt are taken out. The speed of stirring is low. The amount of hexachloroethane is related to the alloy composition and the mass of the original ingot, and is generally 0.5 wt % to 0.7 wt % of the charge. Melting is performed in a resistance furnace, and the refining time is within 10 min.
- Step 5: Slag removing: after fully refining with the hexachloroethane, the bell jar is taken out, the residual oxides are removed, and the inclusions on the surface of the melt are removed with a slag spoon.
- Step 6: Casting: after the alloy slag is removed, pouring should be immediately performed after 4 to 10 min of heat preservation to obtain an alloy ingot for die casting or a die-cast block. The pouring temperature is generally required to be 720 to 750° C.
- Step 7: Die Casting: the above-mentioned alloy ingot for die casting or die-cast block is die-cast into a sample by a conventional semi-solid die casting process, thereby obtaining the aluminum alloy casting of the present disclosure.
- The aluminum alloy and a method for preparing the same of the present disclosure are further described below by way of embodiments. However, the present disclosure is not limited to the embodiments listed below.
- In the following embodiments and comparative examples of the present disclosure, the rare earth element is mixed rare earths (containing 39.8 wt % of La and 58.8 wt % of Ce).
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- The semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 8.5 wt % of Si, 4.0 wt % of Cu, 0.55 wt % of Mn, 0.15 wt % of Ti, 0.20 wt % of rare earth element, and the balance of aluminum.
- The aluminum ingot, the Al—Si intermediate alloy, the Al—Ti intermediate alloy, the Al—Cu intermediate alloy, the Al—Mn intermediate alloy and the Al—Re intermediate alloy ingot measured according to the above semi-solid die-casting aluminum alloy composition were placed into a crucible coated with a covering agent and preheated to 220° C., and were heated and melted after the addition of the covering agent, and the alloys were stirred uniformly after fully melted, where the melting process was 2.5 h, and the final temperature of the aluminum alloy melt was 750° C.; at 700 to 720° C., a bell jar was used to press the refining agent hexachloroethane into about ⅔ below the surface of the melt in batches, and was rotated clockwise uniformly and slowly, for refining for 8 min where the amount of hexachloroethane was 0.5 wt % of the charge; after fully refining, the bell jar was taken out, the residual oxides were removed, and the inclusions on the surface of the melt were removed with a slag spoon; after 5 min of heat preservation, pouring was performed to obtain an aluminum alloy ingot Z1, where the pouring temperature was 750° C.; and the above aluminum alloy ingot Z1 was die-cast into a sample by a conventional semi-solid die casting process, thereby obtaining the aluminum alloy casting Al of this embodiment.
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.5 wt % of Si, 3.5 wt % of Cu, 0.5 wt % of Mn, 0.01 wt % of Ti, 0.01 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A2 of this embodiment.
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 7.5 wt % of Si, 4.8 wt % of Cu, 0.75 wt % of Mn, 0.5 wt % of Ti, 0.35 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A3 of this embodiment.
- This embodiment is for explaining a semi-solid die-casting aluminum alloy and a method for preparing a semi-solid die-casting aluminum alloy casting of the present disclosure.
- The method of Embodiment 1 was employed, except that the semi-solid die-casting aluminum alloy included: based on the total weight of the semi-solid die-casting aluminum alloy, 9.0 wt % of Si, 4.4 wt % of Cu, 0.52 wt % of Mn, 0.10 wt % of Ti, 0.15 wt % of rare earth element and the balance of aluminum, thereby obtaining the aluminum alloy casting A4 of this embodiment.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that no rare earth element was added, thereby obtaining the aluminum alloy casting B1 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that the content of the rare earth element in the semi-solid die-casting aluminum alloy was 0.5 wt %, thereby obtaining the aluminum alloy casting B2 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing the aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that the content of the Si in the semi-solid die-casting aluminum alloy was 10 wt %, thereby obtaining the aluminum alloy casting B3 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that the content of the Si in the semi-solid die-casting aluminum alloy was 7 wt %, thereby obtaining the aluminum alloy casting B4 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing the aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that the content of the Cu in the semi-solid die-casting aluminum alloy was 5 wt %, thereby obtaining the aluminum alloy casting B5 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method and the raw materials of Embodiment 1 were employed except that the content of the Cu in the semi-solid die-casting aluminum alloy was 3 wt %, thereby obtaining the aluminum alloy casting B6 of this comparative example.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method of Embodiment 1 was employed except that a commercially available ADC12 aluminum alloy ingot was used as the ingot, thereby obtaining the aluminum alloy sample B7.
- This comparative example is for explaining a semi-solid die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The method of Embodiment 1 was employed except that a commercially available A356.2 aluminum alloy ingot was used as the ingot, thereby obtaining the aluminum alloy sample B8.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- The raw materials of Embodiment 1 were employed except that a conventional die casting method was used, thereby obtaining the aluminum alloy sample B9.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- Pure aluminum (A00 aluminum), an aluminum-manganese alloy (AlMn10), an aluminum-silicon alloy (AlSi12), an aluminum-iron alloy (AlFe10), an aluminum-copper alloy (Al-50Cu), pure magnesium (99.9), pure zinc (99.95), an aluminum-titanium-carbon-boron alloy, magnesium-lanthanum-cerium (Mg—LaCe) and magnesium-yttrium (Mg—Y) were subjected to mixture calculation, smelting and pouring. The contents of the main elements of the finally obtained alloy were as follows: Si: 6.0 wt %, Cu: 0.5 wt %, Fe: 0.42 wt %, Mn: 0.05 wt %, Mg: 1.0 wt %, Zn: 1.5 wt %, Ti: 0.05 wt %, C: 0.002 wt %, LaCe: 0.20 wt %, Y: 0.12 wt %, and the balance of Al and inevitable impurities. A conventional die casting method was employed to obtain the aluminum alloy sample B10.
- This comparative example is for explaining a die-casting aluminum alloy and a method for preparing an aluminum alloy casting different from the present disclosure.
- (1) A pure magnesium ingot and intermediate alloys Al—Si, Al—Mn, Al—Cu, Al—Ti were preheated to 180 to 240° C., the temperature was kept within the range of 740 to 760° C. after pure aluminum was melted, the pure magnesium ingot and the intermediate alloys Al—Si, Al—Mn, Al—Cu, Al—Ti were sequentially added into the aluminum liquid, and after being melted, they were kept at 740° C. for 30 minutes to be sufficiently homogenized, where the weight percents of the ingredients in the above materials were Si: 8.5 to 11.5%, Mn: 0.1 to 0.8%, Cu: 0.5 to 3.0%, Mg: 0.25 to 0.5%, Ti: 0.15 to 0.35%, and other impurities≤0.4% (where Fe<0.8%, P<0.004%).
- (2) The temperature of the alloy liquid was raised to 780° C., the mixed rare earths were added, the surface scum was removed after the mixed rare earths were melted, the mixture was stirred for 3 to 6 minutes to homogenize the composition, and after stirring, the temperature of the alloy liquid was raised to 770 to 780° C., and then kept to stand for 30 minutes, where the total weight of the mixed rare earths is not more than 1%, and each of La, Ce, Sm and Nd is less than 0.35% by weight.
- (3) After the alloy liquid was cooled to 750° C. and refined for 15 minutes, the alloy liquid was cooled to 710° C. and subjected to slag removal, then the alloy liquid was cooled to 690° C. and subjected to gas removal, finally the alloy liquid after slag removal and gas removal was cooled to at 680° C. and subjected to die casting, and the heat treatment process was performed after the casting was formed. The casting was subjected to solution treatment at a temperature of higher than 545° C. for 3 hours, and then subjected to aging treatment at a temperature of 165° C. for 6 to 12 hours, thereby obtaining the aluminum alloy sample B11.
- Test
- This test was used to determine the mechanical properties of the semi-solid die-casting aluminum alloy castings obtained in Embodiments 1 to 4 and Comparative Examples 1 to 11 at room temperature.
- For the tensile strength, yield strength and elongation of the aluminum alloy castings tested with reference to “GB/T 228.1-2010 Metallic Materials-Tensile Testing-Part 1: Method of test at room temperature”, the specific results are shown in Table 1.
-
TABLE 1 Yield Strength Breaking Strength Elongation Embodiment (MPa) (MPa) (%) Embodiment 1 310 392 8.5 Embodiment 2 300 371 7.0 Embodiment 3 291 376 5.5 Embodiment 4 305 385 8.0 Comparative example 1 254 332 5.5 Comparative example 2 296 367 7.0 Comparative example 3 280 371 6.0 Comparative example 4 261 323 5.0 Comparative example 5 290 342 4.0 Comparative example 6 243 296 5.0 Comparative example 7 185 292 2.5 Comparative example 8 251 310 8.0 Comparative example 9 174 278 2 Comparative example 10 200 300 6.2 Comparative example 11 230 308 5.0 - It can be seen from the comparison of the results of Embodiments 1 to 4 and Comparative Examples 1 to 11 that the semi-solid die-casting aluminum alloy of the present disclosure has good mechanical properties and casting properties, and the semi-solid die-casting aluminum alloy has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%. In particular, the optional alloying elements in the present disclosure include: 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti and 0.15 to 0.25 wt % of rare earth element, the semi-solid die-casting aluminum alloy obtained according to the formula has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%. It can be seen from the comparison of the data of Embodiment 1 and Embodiment 4 with Embodiments 2 to 3 that in the case where the ratio of the weight content of Ti to Cu of the present disclosure is 1:(14 to 90), the semi-solid die-casting aluminum alloy of the present disclosure has better mechanical properties and casting properties.
- Although optional implementations of the present disclosure are described in detail above, the present disclosure is not limited to specific details in the foregoing implementations. Various variations can be made to the technical solutions of the present disclosure within the scope of the technical idea of the present disclosure, and such variations all fall within the protection scope of the present disclosure.
- It should be further noted that the specific technical features described in the foregoing specific implementations can be combined in any appropriate manner provided that no conflict occurs. To avoid unnecessary repetition, various possible combination manners are not further described in the present disclosure.
- In addition, various different implementations of the present disclosure may alternatively be combined randomly. Such combinations should also be considered as the content disclosed in the present disclosure provided that these combinations do not depart from the concept of the present disclosure.
Claims (15)
1. A semi-solid die-casting aluminum alloy, comprising:
alloying elements, inevitable impurities, and a balance of aluminum element,
wherein based on a total weight of the semi-solid die-casting aluminum alloy, the alloying elements comprise:
7.5 to 9.5 wt % of Si,
3.5 to 4.8 wt % of Cu,
0.5 to 0.75 wt % of Mn,
0.01 to 0.5 wt % of Ti, and
0.01 to 0.35 wt % of rare earth element.
2. The semi-solid die-casting aluminum alloy according to claim 1 , wherein based on the total weight of the semi-solid die-casting aluminum alloy, the alloying elements comprise:
8.0 to 9.0 wt % of Si,
3.5 to 4.5 wt % of Cu,
0.5 to 0.6 wt % of Mn,
0.05 to 0.25 wt % of Ti, and
0.15 to 0.25 wt % of rare earth element.
3. The semi-solid die-casting aluminum alloy according to claim 1 , wherein the rare earth element comprises at least one of La, Ce, Pr and Nd.
4. The semi-solid die-casting aluminum alloy according to claim 1 , wherein the impurities in the semi-solid die-casting aluminum alloy are not more than 0.8 wt %.
5. The semi-solid die-casting aluminum alloy according to claim 1 , wherein the ratio of the weight content of Ti to Cu is 1:(14 to 90).
6. The semi-solid die-casting aluminum alloy according to claim 4 , wherein the semi-solid die-casting aluminum alloy comprises 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % Ti, 0.01 to 0.35 wt % of rare earth element, no more than 0.8 wt % of impurities and the balance of aluminum.
7. The semi-solid die-casting aluminum alloy according to claim 6 , wherein the semi-solid die-casting aluminum alloy comprises 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % Ti, 0.15 to 0.25 wt % of rare earth element, no more than 0.7 wt % of impurities and the balance of aluminum.
8. The semi-solid die-casting aluminum alloy according to claim 1 , wherein the semi-solid die-casting aluminum alloy has a tensile strength of not less than 370 MPa, a yield strength of not less than 290 MPa, and an elongation of not less than 5.5%.
9. The semi-solid die-casting aluminum alloy according to claim 2 , wherein the semi-solid die-casting aluminum alloy has a tensile strength of not less than 380 MPa, a yield strength of not less than 300 MPa, and an elongation of not less than 6%.
10. A method for preparing a semi-solid die-casting aluminum alloy casting, comprising:
after performing ratio smelting on aluminum alloy raw materials, performing semi-solid die casting to obtain the semi-solid die-casting aluminum alloy casting,
wherein the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting comprises:
based on the total weight of the aluminum alloy casting, 7.5 to 9.5 wt % of Si, 3.5 to 4.8 wt % of Cu, 0.5 to 0.75 wt % of Mn, 0.01 to 0.5 wt % of Ti, 0.01 to 0.35 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
11. The method according to claim 10 , wherein the aluminum alloy raw materials are such that the obtained semi-solid die-casting aluminum alloy casting comprises: based on the total weight of the semi-solid die-casting aluminum alloy casting, 8.0 to 9.0 wt % of Si, 3.5 to 4.5 wt % of Cu, 0.5 to 0.6 wt % of Mn, 0.05 to 0.25 wt % of Ti, 0.15 to 0.25 wt % of rare earth element, and the balance of aluminum and inevitable impurities.
12. The method according to claim 10 , wherein the aluminum alloy raw material is elemental metals or metal alloys.
13. The method according to claim 12 , wherein the aluminum alloy raw materials are elemental aluminum or an alloy of aluminum, elemental silicon or an alloy of silicon, elemental copper or an alloy of copper, elemental manganese or an alloy of manganese, elemental titanium or an alloy of titanium, and an elemental rare earth element or an alloy containing a rare earth element.
14. The method according to claim 12 , wherein the aluminum alloy raw materials are elemental aluminum, an Al—Si alloy, an Al—Ti alloy, an Al—Cu alloy, an Al—Mn alloy and an Al—Re intermediate alloy.
15. The method according to claim 12 , wherein the purity of the elemental metal is 99.9 wt % or more, and the total content of the alloying elements in the metal alloy is 99.9 wt % or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611096735.4A CN108149083B (en) | 2016-12-02 | 2016-12-02 | A kind of semisolid pressure casting aluminium alloy and the method for preparing semisolid pressure casting aluminium alloy castings |
| CN201611096735.4 | 2016-12-02 | ||
| PCT/CN2017/111382 WO2018099272A1 (en) | 2016-12-02 | 2017-11-16 | Semisolid die-casting aluminum alloy and method for preparing semisolid die-casting aluminum alloy castings |
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| US (1) | US20190390305A1 (en) |
| EP (1) | EP3550046A4 (en) |
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| CN113862528A (en) * | 2021-09-30 | 2021-12-31 | 上海耀鸿科技股份有限公司 | A kind of rare earth aluminum alloy box body material and preparation method and device |
| CN115798778A (en) * | 2022-12-21 | 2023-03-14 | 广东中联电缆集团有限公司 | High-conductivity heat-resistant aluminum alloy conductor and preparation method thereof |
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| CN109396380B (en) * | 2018-11-20 | 2020-12-15 | 吴江市格瑞福金属制品有限公司 | Method for preparing high-heat-conductivity baking tray through semi-solid die-casting |
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| JP3332885B2 (en) * | 1999-04-20 | 2002-10-07 | 古河電気工業株式会社 | Aluminum-based alloy for semi-solid processing and method for manufacturing the processed member |
| US20050161128A1 (en) * | 2002-03-19 | 2005-07-28 | Dasgupta Rathindra | Aluminum alloy |
| JP4765400B2 (en) * | 2005-05-18 | 2011-09-07 | 株式会社豊田中央研究所 | Aluminum alloy for semi-solid casting, aluminum alloy casting and manufacturing method thereof |
| CN102016092A (en) * | 2008-04-30 | 2011-04-13 | 联邦科学和工业研究组织 | Improved Aluminum-Based Casting Alloys |
| JP2011144443A (en) * | 2010-01-18 | 2011-07-28 | Yasuo Sugiura | Aluminum alloy for semisolid casting |
| CN102277520B (en) * | 2010-06-08 | 2012-12-19 | 西安康博新材料科技有限公司 | Aluminium-based material reflector and preparation method thereof |
| CN103526084B (en) * | 2013-09-29 | 2015-06-17 | 宁波东浩铸业有限公司 | Silicone oil clutch |
| CN104831129B (en) * | 2015-04-10 | 2017-03-15 | 凤阳爱尔思轻合金精密成型有限公司 | Non-heat treated is from reinforcing alusil alloy and its preparation technology |
| CN105525158B (en) * | 2016-02-19 | 2018-02-13 | 福建省金瑞高科有限公司 | A kind of semisolid pressure casting aluminum alloy materials and the method using the material die cast |
| CN106086545A (en) * | 2016-08-14 | 2016-11-09 | 林亚东 | A kind of aluminium alloy and preparation method thereof |
-
2016
- 2016-12-02 CN CN201611096735.4A patent/CN108149083B/en active Active
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- 2017-11-16 WO PCT/CN2017/111382 patent/WO2018099272A1/en not_active Ceased
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| CN113862528A (en) * | 2021-09-30 | 2021-12-31 | 上海耀鸿科技股份有限公司 | A kind of rare earth aluminum alloy box body material and preparation method and device |
| CN115798778A (en) * | 2022-12-21 | 2023-03-14 | 广东中联电缆集团有限公司 | High-conductivity heat-resistant aluminum alloy conductor and preparation method thereof |
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| EP3550046A4 (en) | 2020-08-05 |
| CN108149083A (en) | 2018-06-12 |
| EP3550046A1 (en) | 2019-10-09 |
| CN108149083B (en) | 2019-11-05 |
| WO2018099272A1 (en) | 2018-06-07 |
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