EP3301198B1 - Aluminum alloy for die casting and method for manufacturing the same - Google Patents

Aluminum alloy for die casting and method for manufacturing the same Download PDF

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Publication number
EP3301198B1
EP3301198B1 EP17192766.8A EP17192766A EP3301198B1 EP 3301198 B1 EP3301198 B1 EP 3301198B1 EP 17192766 A EP17192766 A EP 17192766A EP 3301198 B1 EP3301198 B1 EP 3301198B1
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Prior art keywords
aluminum alloy
die casting
alloy
present disclosure
aluminum
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German (de)
English (en)
French (fr)
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EP3301198A1 (en
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Sung-Tae Park
Won JU
Jung-Soo Lim
Jeong-Su Han
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • 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
    • 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
    • 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
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions

Definitions

  • Apparatuses and methods consistent with the present disclosure relate to an aluminum alloy for die casting, and more particularly, to an aluminum alloy for die casting including, by wt%, 3 ⁇ Si ⁇ 10, 3 ⁇ Mg ⁇ 10, 0.01 ⁇ Fe ⁇ 1.3, 0.01 ⁇ Zn ⁇ 2, 0.01 ⁇ Cu ⁇ 1.5, 0.01 ⁇ Mn ⁇ 0.5, 0.05 ⁇ Ti ⁇ 0.15, 0.01 ⁇ La ⁇ 2, 0.01 ⁇ Sr ⁇ 2, a balance of Al, and unavoidable impurities, and having improved mechanical properties and corrosion resistance.
  • a die casting method is widely used, and the die casting is precision casting to inject a molten metal into a mold which was precisely machined to a casting shape, thereby obtaining the same casting as the mold.
  • the produced product has correct dimensions, and thus, does not need to be ironed, and has excellent mechanical properties, and with high mass productivity due to a mass production possibility and a low production cost, this method is currently most used in various fields such as automotive parts, electrical equipment, optical instruments and measuring instruments.
  • WO2016068494 discloses an aluminum alloy for die-casting comprising 6 to 8.5 wt% of Mg, 4 to 6 wt% of Si, 0.4 to 0.8 wt% of Fe, 0.2 to 0.5 wt% of Mn, 0.01 to 0.1 wt% of Cu, 0.05 to 0.15 wt% of Ti, and the remainder being Al.
  • CN105970038 discloses an aluminum alloy profile comprising 3-5% of Mg, 2-3.5% of Si, 0.2-0.8% of Ni, 1-1.5% of Sr, 0.47-1.88% of La and the balance of Al.
  • an Al-Si-based alloy such as ALDC 3, ALDC 10 or ALDC 12, and an Al-Mg alloy such as ALDC 5 or ALDC 6, which have good castability have been used.
  • these aluminum die casting materials have problems in that pores occur in the inside due to air ingress during die casting, mechanical properties are degraded due to occurrence of the pores, when magnesium is contained in a large amount, a molten metal is deposited on the mold surface to shorten the mold life, and the processing time is increased and a tool is damaged due to chip curling during processing.
  • the aluminum die casting materials have poor corrosion resistance, they have limited expansion of coverage.
  • a method of forming a protective coated film on the alloy surface using a physical deposition has been suggested, however, this method has problems in that it needs expensive supplementary equipment, and is difficult to be recycled.
  • Other methods have been suggested, such as ion implantation to implant the ions of elements having corrosion resistance in the alloy surface and laser annealing to inject laser into the alloy surface to form a metastable state on the surface layer.
  • the former has a limitation in an ion implantation depth and, thus, corrosion resistance is rapidly deteriorated when the ion implantation layer is damaged during use.
  • the latter needs separate machining since the size of the product is changed during a treatment process.
  • the need for a new aluminum alloy for die casting arises, the aluminum alloy having excellent mechanical properties and corrosion resistance, and not having a deposit on the mold surface in the course of die casting, even in the case of containing a large amount of magnesium.
  • an alloy for die casting including lanthanum (La) and strontium (Sr) to have improved mechanical properties and corrosion resistance, and a method for manufacturing the same.
  • the aluminum alloy for die casting according to an exemplary embodiment of the present disclosure includes, by wt%, 3 ⁇ Si ⁇ 10, 3 ⁇ Mg ⁇ 10, 0.01 ⁇ Fe ⁇ 1.3, 0.01 ⁇ Zn ⁇ 2, 0.01 ⁇ Cu ⁇ 1.5, 0.01 ⁇ Mn ⁇ 0.5, 0.05 ⁇ Ti ⁇ 0.15, 0.01 ⁇ La ⁇ 2, 0.01 ⁇ Sr ⁇ 2, a balance of Al, and unavoidable impurities.
  • an aluminum flange shaft for a washing machine may be manufactured from the alloy for die casting according to an exemplary embodiment of the present disclosure.
  • a method for manufacturing the aluminum alloy for die casting includes: preparing a parent alloy including La and Sr; melting Al, Si, Mg, Fe, Zn, Cu, Mn and Ti in a crucible to include, by wt%, 3 ⁇ Si ⁇ 10, 3 ⁇ Mg ⁇ 10, 0.01 ⁇ Fe ⁇ 1.3, 0.01 ⁇ Zn ⁇ 2, 0.01 ⁇ Cu ⁇ 1.5, 0.01 ⁇ Mn ⁇ 0.5 and 0.05 ⁇ Ti ⁇ 0.15, based on the total weight of the aluminum alloy for die casting; and adding the thus-prepared parent alloy to the crucible to include, by wt%, 0.01 ⁇ La ⁇ 2 and 0.01 ⁇ Sr ⁇ 2, based on the total weight of the aluminum alloy for die casting.
  • adding flux to the crucible may be further included.
  • the parent alloy may be an Al-La-Sr ternary parent alloy, or an Al-Mg-La-Sr quaternary parent alloy.
  • the melting may be carried out at 600 to 700 °C.
  • FIGS. 1A through 5 discussed below, and the various embodiments used to describe the principles of the present disclosure in this patent document are by way of illustration only and should not be construed in any way to limit the scope of the claims. Those skilled in the art will understand that the principles of the present disclosure may be implemented in any suitably arranged system or device.
  • the aluminum alloy for die casting of the present disclosure includes 3 to 10 wt% of silicon (Si), 3 to 10 wt% of magnesium (Mg), 0.01 to 1.3 wt% of iron (Fe), 0.01 to 2 wt% of Zinc (Zn), 0.01 to 1.5 wt% of copper (Cu), 0.01 to 0.5 wt% of manganese (Mn), 0.05 to 0.15 wt% of titanium (Ti), 0.01 to 2 wt% of lanthanum (La), 0.01 to 2 wt% of strontium (Sr), a balance of Al, and unavoidable impurities.
  • the unavoidable impurities included in the alloy may be in a trace amount, and incidental impurities which may be present therein may be B, Cr, Sn, Sr, Pb, Ni, Cd, Ag, Zr, Ca, Mo, other transition metal elements, another rare earth elements, or the like, but not limited thereto.
  • incidental impurities may be varied with the castings, but their presence does not have an influence on the present disclosure, and the total amount of impurities may be less than 0.01 wt%.
  • the aluminum alloy for die casting of the present disclosure includes 3 to 10 wt% of magnesium (Mg).
  • the magnesium component improves tensile strength and also is lighter than Si, thereby being advantageous for weight reduction of a product.
  • the content of magnesium is less than 3 wt%, the effect of increasing tensile strength may not be obtained, and in the case that the content of magnesium is more than 10 wt%, corrosion resistance is deteriorated and stickiness of a molten metal is increased to lower fluidity, leading to deteriorated workability.
  • the aluminum alloy of the present disclosure includes a significantly large amount of magnesium as compared with a conventional Al-Si-based alloy, which is larger than the amount of magnesium in an Al-Mg-based alloy.
  • Such magnesium amount of the present disclosure has a technical significance in that the purpose of higher strength of a product may be achieved, while corrosion resistance and workability are not deteriorated. Due to these characteristics, the alloy of the present disclosure may be applied to the parts of household appliances demanding both strength and high corrosion resistance, and particularly, is advantageous for products which impact is repeatedly applied to and is in contact with water or air.
  • the aluminum alloy according to the present disclosure may be used in the parts such as a flange shaft fixing the drum of a washing machine to be rotated.
  • the aluminum alloy for die casting of the present disclosure includes silicon (Si).
  • the Si component improves the fluidity of the aluminum alloy to improve moldability, lowers a coagulation shrinkage rate to reduce a shrinkage amount, and serves to improve hardness.
  • Si can be added in an amount of 3 to 10 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure. In the case that the content of Si component is less than 3 wt%, the addition effect is negligible, whereas in the case that the content of Si component is more than 10 wt%, a thermal expansion coefficient and an elongation may be lowered, and stains may occur on the surface.
  • the aluminum alloy for die casting of the present disclosure includes iron (Fe).
  • the Fe component reduces adhesion in the mold for die casting to have good castability, and serves to deteriorate erosion of the mold.
  • Fe can be added in an amount of 0.01 to 1.3 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the content of Fe component is less than 0.01 wt%, based on the total weight of the whole alloy, it is difficult to release the cast article, whereas in the case that the content of Fe component is more than 1.3 wt%, Al and Si may be bonded to produce vulnerable precipitates, and decrease the corrosion resistance of the aluminum alloy.
  • the aluminum alloy for die casting of the present disclosure includes zinc (Zn).
  • the Zn component has an effect of improving strength and castability of an alloy.
  • Zn can be added in an amount of 0.01 to 2 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the content of Zn component is less than 0.01 wt%, based on the total weight of the whole alloy, the improvement of the mechanical properties is negligible, whereas in the case that the content of Zn component is more than 2 wt%, the density of alloy is reduced to cause cracks.
  • the aluminum alloy for die casting of the present disclosure includes manganese (Mn).
  • the Mn component serves to precipitate a Mn-Al6 phase in the alloy to improve the mechanical properties of the alloy by solid solution strengthening and dispersion of fine precipitates.
  • Mn can be added in an amount of 0.01 to 0.5 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the improvement of the mechanical properties is negligible, whereas in the case that the content of Mn component is more than 0.5 wt%, the workability may be deteriorated due to adhesion, which is also caused by Mg.
  • the aluminum alloy for die casting of the present disclosure includes copper (Cu).
  • the Cu component has an effect of improving strength and hardness of an alloy.
  • Cu can be added in an amount of 0.01 to 1.5 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the content of Cu component is less than 0.01 wt%, based on the total weight of the whole alloy, the improvement of the mechanical properties is negligible, whereas in the case that the content of Cu component is more than 1.5 wt%, corrosion resistance and an elongation may be deteriorated.
  • the aluminum alloy for die casting of the present disclosure includes titanium (Ti).
  • Ti titanium
  • the Ti component may be added to the aluminum alloy to serve to refine crystal grains, and obtain a crack prevention effect, and Ti can be added in an amount of 0.05 to 0.15 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the content of Ti component is less than 0.05 wt%, the effect of crystal grain refining may not be obtained, whereas in the case that the content of Ti component is more than 0.15 wt%, the elongation may be decreased.
  • the aluminum alloy for die casting of the present disclosure includes lanthanum (La).
  • the La component is added to the aluminum alloy to have effects of improving the fluidity of the aluminum alloy to improve moldability, improving the deposition properties of the melted alloy on the mold, and improving the corrosion resistance.
  • La has an effect of stabilizing a microcrystalline phase in an aluminum matrix by forming an intermetallic compound with an alloy element such as Cu and Fe.
  • La can be added in an amount of 0.01 to 2 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • La can be included at 0.01 to 0.5 wt%, based on the total weight of the whole alloy.
  • the aluminum alloy for die casting of the present disclosure includes strontium (Sr).
  • the Sr component may have an effect of improving the strength of an alloy by reducing pores produced by air ingress in the course of die casting, and Sr can added in an amount of 0.01 to 2 wt%, based on the total weight of the whole alloy, in the aluminum alloy for die casting of the present disclosure.
  • the content of Sr component is less than 0.01 wt%, the improvement of the mechanical properties is negligible, whereas in the case that the content of Sr component is more than 2.0 wt%, the distribution of pores is decreased, but the size of pores is increased.
  • Sr can be included at 0.05 to 1.0 wt%, based on the total weight of the whole alloy.
  • Sr also can be included at 0.1 to 0.5 wt%, based on the total weight of the whole alloy.
  • Each component such as aluminum, silicon, iron, copper and titanium, can have a purity of at least about 99%.
  • the aluminum alloy for die casting of the present disclosure includes a large amount of Mg (magnesium) as compared with the conventional aluminum alloy of die casting, it has an effect of improving corrosion resistance. Further, the aluminum alloy for die casting of the present disclosure is not deposited on the mold, and thus, is easily worked, may increase the mold life, and reduces pores produced in the course of die casting to improve mechanical properties such as strength, internal force and an impact value. Accordingly, the problems of increased processing time and damaged processing tools due to chip curling during processing the conventional aluminum alloy may be solved.
  • Mg manganesium
  • an aluminum alloy for die casting having excellent corrosion resistance and mechanical properties was manufactured from silicon, iron, copper, manganese, magnesium, strontium, lanthanum, zinc, titanium and aluminum to have the composition as shown in the following Table 1 (Example). The specific method of manufacturing the aluminum alloy for die casting is described in detail with reference to the following FIG. 5 .
  • an ADC 12 alloy having the composition as shown in the following Table 1 (ADC 12 (found)) was manufactured.
  • Alloy (wt%) Si Fe Cu Mn Mg Sr La Zn Ti Al ADC 12 (average) 9.6-12.0 ⁇ 1.3 1.5-3.5 ⁇ 0.5 ⁇ 0.3 - - ⁇ 1.0 ⁇ 0.3 balance
  • ADC 12 (found) 10.7 0.89 1.76 0.19 0.17 - - 0.7 0.02 balance
  • Example 6.5 0.8 1.0 0.1 6.0 0.15 0.3 0.8 0.1 balance
  • the aluminum alloy as the Example according to the present disclosure manufactured to have the composition as shown in the above Table 1, and ADC 12 as the Comparative Example were dissolved, respectively, maintained at 600 to 700 °C, and then according to the known method, were added to a mold using die casting equipment and subjected to injection and cooling, thereby preparing each specimen.
  • Each specimen after being die cast was immersed in a potassium hydroxide (KOH) solution having a pH of 10 to 11 at 25 °C for 480 hours, and then the surface of each specimen was analyzed using a digital microscope.
  • KOH potassium hydroxide
  • FIGS. 1A and 1B represent analysis of the surface of the specimen formed of ADC 12 which is the conventional aluminum alloy for die casting. Specifically, FIGS. 1A and 1B are magnifications of 50 times and 200 times the surface of the specimen, respectively. Further, FIGS. 2A and 2B represent analysis of the surface of the specimen of the aluminum alloy for die casting manufactured to have the composition as shown in Table 1 according to an exemplary embodiment of the present disclosure. Specifically, FIGS. 2A and 2B are magnifications of 50 times and 200 times the surface of the specimen, respectively.
  • pitting corrosion occurred on the surface of the specimen formed of ADC 12.
  • the pitting corrosion has a depth of 60 to 100 ⁇ m.
  • exfoliation corrosion was also found in the specimen formed of ADC 12.
  • the pitting corrosion has a small number and a shallow depth on the surface of the manufactured specimen having the composition according to an exemplary embodiment of the present disclosure.
  • the aluminum alloy for die casting according to an exemplary embodiment of the present disclosure including La and Sr has excellent corrosion resistance, despite its higher content of Mg than the conventional aluminum alloy for die casting.
  • the aluminum alloy as the Example according to the present disclosure manufactured to have the composition as shown in the above Table 1, and ADC 12 as the Comparative Example were dissolved, respectively, maintained at 600 to 700 °C, and then added to a mold using die casting equipment and subjected to injection and cooling, thereby preparing each specimen.
  • Each specimen after being die cast was cut into an exposure area of 1 cm 2 , and then the corrosion durability of the specimen was evaluated by a potentiodynamic polarization experiment in an environment comprising 5% sodium chloride (NaCl).
  • the potentiodynamic polarization experiment is an experiment using polarity determined by an electrical displacement difference produced in the course of electricity generation, and current, voltage, resistance or the like have been analyzed by the experiment.
  • the corrosion current (I corr ) of the specimen formed of the aluminum alloy according to an exemplary embodiment of the present disclosure is 4.12 ⁇ A, which means that the specimen has corrosion durability three times more than that of the specimen formed of ADC 12.
  • the specimen formed of the aluminum alloy according to an exemplary embodiment of the present disclosure represents corrosion resistance (Z re ) 1.7 times more than that of the specimen formed of ADC 12, and thus, have been confirmed to have better corrosion durability as compared with that of the conventional aluminum alloy for die casting.
  • the value representing the corrosion durability in the following Table 2 is only an example, and thus, not limited thereto, and the aluminum alloy according to the present disclosure may have a corrosion current of 3.5 to 4.5 ⁇ A, a potential of -660 to -645 V, and a corrosion resistance of 4.9 to 5.6 ⁇ , depending on the change in the content of each component.
  • [Table 2] Classification I corr [ ⁇ A] E [mV] Zre [ ⁇ ] ADC 12 12.68 -608 3.1
  • FIGS. 3A to 3D are drawings representing the corrosion resistance experiment results of ADC 12 which is the conventional aluminum alloy for die casting and the aluminum alloy for die casting manufactured according to the present disclosure, depending on the content of Sr.
  • the Comparative Example illustrated in FIG. 3A was prepared from ADC 12 having the composition as shown in the above Table 1
  • the Example according to the present disclosure illustrated in FIGS. 3B to 3D was prepared by changing the content of Sr in the composition as shown in the above Table 1 into 0 wt%, 0.15 wt% and 0.5 wt%, respectively.
  • the pore size is the smallest when the content of Sr is 0.15 wt%. Further, the pore size when the content of Sr was 0 wt% was 5 to 10 ⁇ m as illustrated in FIG. 3B , however, the pore size when the content of Sr was 0.15 wt% was decreased to less than 5 ⁇ m, as illustrated in FIG. 3C . Accordingly, it is recognized that the aluminum alloy for die casting according to an exemplary embodiment of the present disclosure including La and Sr has excellent corrosion resistance, despite its higher content of Mg than the conventional aluminum alloy for die casting.
  • the pore distribution was the smallest. As illustrated in FIG. 3D , however, the pore size was increased as compared with the pore size when the content of Sr is 0.15 wt%. Thus, the content of Sr can be about 0.15 wt%.
  • the aluminum alloy as the Example according to the present disclosure manufactured to have the composition as shown in the above Table 1, and ADC 12 as the Comparative Example were dissolved, respectively, maintained at 600 to 700 °C, and then, according to the known method, were added to a mold using die casting equipment and subjected to injection and cooling, thereby preparing each specimen.
  • Each specimen after being die cast was cut into 2.9 mm x 23.7 mm, and tensile strength, yield strength, a deformation amount, internal force, an impact value and the like of the specimen were measured according to ASTM standards, using a universal testing machine.
  • FIGS. 4A to 4C are drawings for comparing and describing the strength of Al 6061 which is the conventional aluminum alloy and the aluminum alloy manufactured according to the present disclosure. Specifically, each of FIGS. 4A to 4C represents fragments produced when processing the conventional Al 6061, brass and the alloy according to the present disclosure.
  • Al 6061 and brass are commercially available alloy products.
  • chip curling refers to curling of the fragments produced from alloy processing without falling off on a tool, and this causes increased processing time and shortened tool life.
  • brass has high strength and hardness, fragments occur in the form of powder when alloy processing, and thus, chip curling does not occur, as illustrated in FIG. 4B .
  • the fragments produced when processing the aluminum alloy according to the present disclosure are in the form of powder, similarly to FIG. 4B .
  • the aluminum alloy according to the present disclosure has improved hardness and strength as compared with Al 6061, the conventional aluminum alloy, and has reduced chip curling, and thus, the shortened processing time of the alloy and the prolonged tool life may be expected.
  • FIG. 5 is a flow chart for describing a process of manufacturing the aluminum alloy for die casting according to the present disclosure.
  • a parent alloy including La and Sr is prepared (S501). Specifically, La and Sr are added to Al according to the composition, and melted together at 600 to 700 °C to prepare an Al-La-Sr ternary parent alloy.
  • Mg is further added to prepare an Al-Mg-La-Sr quaternary parent alloy.
  • the components other than La and Sr in the aluminum alloy of the present disclosure is added to a crucible according to the composition, and melted at 600 to 700 °C (S520).
  • Al, Si, Mg, Fe, Zn, Cu, Mn and Ti is added to the crucible to include, by wt%, 3 ⁇ Si ⁇ 10, 3 ⁇ Mg ⁇ 10, 0.01 ⁇ Fe ⁇ 1.3, 0.01 ⁇ Zn ⁇ 2, 0.01 ⁇ Cu ⁇ 1.5, 0.01 ⁇ Mn ⁇ 0.5 and 0.05 ⁇ Ti ⁇ 0.15, based on the total weight of the aluminum alloy for die casting.
  • the crucible may be a graphite crucible. Meanwhile, after completing the melting, a process of adding flux to form an oxidation prevention film on the molten metal surface is further carried out.
  • the thus-prepared parent alloy is added to the molten metal according to the composition, and melted together (S530).
  • the parent alloy prepared to include, by wt%, 0.01 ⁇ La ⁇ 2 and 0.01 ⁇ Sr ⁇ 2, based on the total weight of the aluminum alloy for die casting is added to the molten metal.
  • the parent alloy is heated to 600 to 700 °C for 30 to 60 minutes to be completely dissolved.
  • the molten alloy is added to a mold using die casting equipment according to a known method, and subjected to injection and cooling to produce a product.
  • the alloy may be manufactured more stably without losing components, by preparing the aluminum alloy using the parent alloy including La and Sr.
  • the present disclosure is not limited thereto, and after melting the aluminum alloy not including La and Sr, the parent alloy including La and Sr may be prepared, or the two processes may be carried out simultaneously or individually.
  • the aluminum alloy having excellent fluidity to be easily cast, having a little deposit on the mold surface, and having improved mechanical properties and corrosion resistance is obtained, by including La and Sr in the aluminum alloy.
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KR102597784B1 (ko) * 2018-08-24 2023-11-03 삼성전자주식회사 다이캐스팅용 알루미늄 합금 및 그 제조방법, 다이캐스팅 방법
KR102634398B1 (ko) * 2018-12-10 2024-02-06 현대자동차주식회사 피스톤용 알루미늄 합금 및 차량 엔진용 피스톤
KR101992201B1 (ko) * 2019-02-21 2019-06-24 엘지전자 주식회사 다이캐스팅용 알루미늄 합금 및 다이캐스팅 주물
CN110408824A (zh) * 2019-09-03 2019-11-05 中国工程物理研究院机械制造工艺研究所 一种适用于3d打印的高强铝合金
KR102364642B1 (ko) * 2020-02-06 2022-02-18 주식회사 에스피텍 실리콘과 아연이 첨가된 고강도 다이캐스팅용 알루미늄 합금 및 그 제조방법
CN111647784A (zh) * 2020-06-17 2020-09-11 帅翼驰新材料集团有限公司 高导热高强度压铸铝合金及其制备方法
CN114381639A (zh) * 2022-01-07 2022-04-22 山东创新精密科技有限公司 一种船舶用高强耐蚀铝合金及其制备方法
CN114438378A (zh) * 2022-01-14 2022-05-06 大连理工大学宁波研究院 一种新能源汽车一体化成型铝硅合金及其制备方法
CN115181878B (zh) * 2022-09-14 2022-12-23 苏州慧金新材料科技有限公司 新能源汽车用一体式压铸件铝合金及制备方法和应用

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5815390B2 (ja) * 1974-11-08 1983-03-25 帝人株式会社 タカクケイパイルノ シユウゴウコンポウホウホウ
JPH05179384A (ja) * 1991-12-27 1993-07-20 Honda Motor Co Ltd 噴霧堆積法により製造された高強度高靭性アルミニウム合金
JPH05332364A (ja) * 1992-06-01 1993-12-14 Daido Metal Co Ltd 耐摩耗性に優れたアルミニウム合金軸受およびその製造方法
US6334978B1 (en) * 1999-07-13 2002-01-01 Alcoa, Inc. Cast alloys
DE60231046D1 (de) * 2001-07-25 2009-03-19 Showa Denko Kk Aluminiumlegierung mit hervorragender zerspanbarkeit und aluminiumlegierungsmaterial und herstellungsverfahren dafür
CN101514420A (zh) * 2009-04-13 2009-08-26 清华大学 汽车轮毂用铝合金
KR101083750B1 (ko) * 2009-04-13 2011-11-16 동부제철 주식회사 알루미늄계 합금도금욕과 이를 도금한 합금도금 강재
KR100978558B1 (ko) * 2009-09-28 2010-08-27 최홍신 고강도 알루미늄-마그네슘계 합금 제조방법
US8758529B2 (en) * 2010-06-30 2014-06-24 GM Global Technology Operations LLC Cast aluminum alloys
CN102925763A (zh) * 2011-08-11 2013-02-13 赵凯志 铝合金汽车轮毂复合强化技术
CN103374673A (zh) * 2012-04-24 2013-10-30 台山市国际交通器材配件有限公司 一种铸造铝合金轮毂的配方
US10053753B2 (en) * 2013-02-28 2018-08-21 Nippon Steel & Sumikin Coated Sheet Corporation Aluminum-zinc plated steel sheet and method for producing the same
CN103334034B (zh) * 2013-06-14 2016-05-25 宁波科达制动器制造有限公司 一种涡轮增压器压气机蜗壳的制备方法
CN103789582A (zh) * 2014-01-09 2014-05-14 马鞍山市恒毅机械制造有限公司 一种轿车轮毂专用铝硅镁合金材料及其制备方法
KR101641170B1 (ko) * 2014-09-02 2016-07-20 삼성전자주식회사 다이캐스팅용 알루미늄 합금 및 그 제조 방법
KR101620204B1 (ko) * 2014-10-15 2016-05-13 현대자동차주식회사 다이캐스팅 부품용 합금 및 그 제조방법
KR101606525B1 (ko) * 2014-10-29 2016-03-25 주식회사 케이엠더블유 내식성이 개선된 다이캐스팅용 알루미늄 합금
CN105441737A (zh) * 2015-12-01 2016-03-30 上海交通大学 高强、高耐腐蚀铸造铝合金及其重力铸造制备方法
CN105970038B (zh) * 2016-07-20 2017-11-21 仪征海天铝业有限公司 一种具有良好导电性能的铝合金型材及其加工方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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US20180087132A1 (en) 2018-03-29
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EP3301198A1 (en) 2018-04-04
KR102591353B1 (ko) 2023-10-20

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