WO2022139007A1 - Alliage d'aluminium pour coulée à ténacité élevée et son procédé de fabrication - Google Patents

Alliage d'aluminium pour coulée à ténacité élevée et son procédé de fabrication Download PDF

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WO2022139007A1
WO2022139007A1 PCT/KR2020/018860 KR2020018860W WO2022139007A1 WO 2022139007 A1 WO2022139007 A1 WO 2022139007A1 KR 2020018860 W KR2020018860 W KR 2020018860W WO 2022139007 A1 WO2022139007 A1 WO 2022139007A1
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aluminum alloy
casting
alloy
high toughness
content
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PCT/KR2020/018860
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Korean (ko)
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손희식
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주식회사 에프티넷
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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
    • 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
    • C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent

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  • the present invention relates to an aluminum alloy for casting with high toughness, and more specifically, by adding silicon (Si) and rare earth elements to the alloy for casting, while maintaining the fluidity of the alloy for casting, strength, toughness, corrosion resistance and releasability are improved. It relates to an aluminum alloy for casting of high toughness and a method for manufacturing the same.
  • the alloy for aluminum casting is indicated by the sign of AC (Aluminum Casting), and the alloy for die casting is indicated by the sign of ALDC (Aluminum Die Casting) and is widely used.
  • the tensile strength is high in the range of 300 MPa to 400 MPa, but the elongation is mostly in the range of about 1%, so the toughness is extremely insufficient.
  • the ADLC series has a tensile strength in the range of 200 MPa to 300 MPa, and the elongation is mostly about 3% or less, so it also lacks toughness.
  • Alloy AC4A alloy for casting which has a composition similar to ALDC 3, is also widely used.
  • the Patent Document 1 is referred to as Prior Art 1 from now on, and the contents are as follows.
  • This prior art 1 is a patent document whose rights have expired due to the expiration of the duration.
  • the content of the aluminum alloy composition is 9.5 to 11.5 wt% of silicon (Si), 0.1 to 0.5 wt% of magnesium (Mg), 0.5 to 0.8 wt% of manganese (Mn), 30 to 300 ppm of strontium (Sr), and 0.05 It consists of ⁇ 0.3wt% of zirconium (Zr), additionally 0.15wt% or less of iron (Fe), 0.03wt% or less of copper (Cu), 0.10wt% or less of zinc (Zn) and 0.15wt% or less of titanium (Ti) include
  • the above prior art 1 is an improved alloy of commercial alloys ALDC3 and AC4A. It was applied for in 1995, and although its duration has expired, it has made a partial contribution to the field of aluminum alloy for casting, and has increased the tensile strength to more than 300 MPa while maintaining castability. However, the ductility was somewhat sacrificed, and the corrosion resistance was not improved. In particular, the commercial alloy and prior art 1 lack a lot of releasability with the mold after casting the mold.
  • Patent Document 2 the composition is a document in which the composition is continuously modified based on the commercial alloy and prior art 1.
  • Patent Document 2 has a purpose of sacrificing strength and increasing ductility based on the prior art 1. That is, by reducing the content of magnesium (Mg), the aging hardening effect is abandoned to increase the ductility.
  • Mg magnesium
  • the present invention relates to an aluminum alloy more improved based on the commercial alloys ALDC3 and AC4A and the above prior art 1, and by adding rare earth metals such as cerium (Ce) or lanthanum (La), corrosion resistance and mold release properties are greatly improved.
  • rare earth metals such as cerium (Ce) or lanthanum (La)
  • Ce cerium
  • La lanthanum
  • An object of the present invention for the above problems is to solve all the problems described above in relation to the aluminum alloy for casting and die casting.
  • An object of the present invention is to provide an aluminum alloy composition for casting or die casting having high toughness with high strength, ductility, corrosion resistance, castability and releasability, and a method for manufacturing the same.
  • An aluminum alloy for casting comprising:
  • any one of rare earth metals having atomic numbers 57 (La) to 71 (Lu) or a combination thereof, including lanthanum (La) and cerium (Ce), is in the range of 0.0001 to 3.0 wt%;
  • the remainder provides an aluminum alloy for casting with high toughness, characterized in that it contains; aluminum (Al) and unavoidable impurities.
  • the aluminum alloy is rapidly cooled after heat treatment at 350 to 550° C. for 1 hour to 10 hours, and then aging heat treatment is performed again at 100 to 200° C. for 1 hour to 10 hours. It is characterized in that it is manufactured.
  • the aluminum alloy was comprehensively limited in the content of silcone (Si), more specifically, it would be preferable to select one from 8.0 to 10.0 wt%, 9.0 to 11.0 wt%, or 9.50 to 11.50 wt%.
  • magnesium (Mg) is limited in the aluminum alloy, it will be preferable to select one from 0.30 to 0.60 wt%, 0.40 to 0.60 wt%, or 0.10 to 0.50 wt%.
  • the Mn content of the aluminum alloy is preferably selected from among 0.30 to 0.60 wt%, 0.0001 to 0.30 wt%, or 0.50 to 0.80 wt%.
  • composition in which the content of Fe in the aluminum alloy is 0.55 wt% or less or 0.15 wt% or less.
  • the aluminum alloy is preferably composed by selecting the Ti content in the range of 0.20 wt% or less or 0.15 wt% or less.
  • the aluminum alloy preferably has a content of cerium (Ce) in the range of 0.05 to 1.5 wt%.
  • the content of lanthanum (La) is preferably in the range of 0.05 to 1.5 wt%.
  • the aluminum alloy is characterized in that it further comprises strontium (Sr) selected from the range of 0.0001 to 0.045 wt%, 0.003 to 0.030 wt%, or 0.005 to 0.015 wt%, based on the total weight.
  • strontium selected from the range of 0.0001 to 0.045 wt%, 0.003 to 0.030 wt%, or 0.005 to 0.015 wt%, based on the total weight.
  • the aluminum alloy is an aluminum alloy for high toughness casting, characterized in that it further comprises zirconium (Zr) selected within the range of 0.0001 to 0.30 wt% or 0.05 to 0.30 wt% based on the total weight.
  • Zr zirconium
  • the aluminum alloy is characterized in that the phosphorus (P) component is further added in the form of any one of gallium phosphide, indium phosphide, or a combination thereof, in a weight ratio of 0.0001 to 0.0250 wt% or 0.0001 to 0.0030 wt%.
  • the aluminum alloy preferably further comprises 0.0001 to 0.50 wt% or 0.05 to 0.50 wt% of molybdenum (Mo).
  • the aluminum alloy of the present invention is one selected from Cr, V, Ni, In, Pb, Bi, Ca, Na, P, B, Ag, Pd, Sb, Sc, Nb, Co, Mo, Be, Hf or Y
  • an aluminum alloy for high toughness casting can be manufactured.
  • the aluminum alloy is in the range of 0.0001 to 0.50 wt% ZrO 2 , SiO 2 , Al 2 O 3 , Y 2 O 3 CeO 2 , La 2 O 3 Or further comprising any one of a combination thereof, characterized in that the oxide is uniformly dispersed in the state of nano-sized particles in the alloy.
  • any one of these combinations is characterized in that the master alloy of aluminum and oxide is made and the master alloy is put into the molten metal.
  • the present invention is basically an improvement of ALDC3, AC4A and prior art 1, and in particular, by adding rare earth elements such as cerium (Ce) and lanthanum (La), corrosion resistance and releasability are greatly improved.
  • rare earth elements such as cerium (Ce) and lanthanum (La)
  • corrosion resistance and releasability are greatly improved.
  • the strength and toughness can be improved by adding zirconium (Zr) in the form of fine nano-sized particles. Due to this, it is possible to greatly expand the applications of aluminum alloys for casting or die casting.
  • 1 is a characteristic graph of measuring mechanical properties among data measuring tensile strength, yield strength, elongation, hardness, corrosion resistance, and releasability of an alloy according to the present invention
  • the content indication in the present invention is a ratio with respect to the total weight of the aluminum alloy. All content indications in the description and claims of the present invention are also the same.
  • the main alloying elements in aluminum alloys are silicon (Si), manganese (Mn), magnesium (Mg), copper (Cu), zinc (Zn), iron (Fe), titanium (Ti), strontium (Sr), and zirconium (Zr). ), molybdenum (Mo) and rare earth elements such as cerium (Ce) and lanthanum (La) have the following effects on the properties of the alloy.
  • Si is a major component that increases the fluidity of the alloy in the molten state during the die casting process. When an appropriate amount is added, the melting point decreases, thereby improving castability and increasing fluidity. However, when it is added excessively, the fluidity deteriorates. In addition, as the content of Si increases, it acts as an element to improve fatigue strength, hardness and wear resistance, but reduces ductility and impact resistance. When coexisting with magnesium (Mg), Mg 2 Si may be formed to improve strength by aging treatment.
  • Mg 2 Si may be formed to improve strength by aging treatment.
  • a preferred range in the present invention is 8.0 to 11.5 wt%, and a more preferred range is 8.0 to 10.0 wt% or 9.0 to 11.0 wt% or 9.5 to 11.5 wt%.
  • Magnesium (Mg) improves mechanical strength by a solid solution effect, and aging strengthening characteristics may occur depending on the coexistence of silicon (Si) and zinc (Zn). Machinability is improved, corrosion resistance to seawater is improved, and solidification shrinkage is reduced. Weldability and surface finish properties are also improved. However, since the fluidity of the molten metal is weakened and the bond with oxygen is particularly strong, care must be taken to introduce oxides. If the content is more than an appropriate amount, the fluidity deteriorates, and if it is added more than that, die casting becomes difficult, and microbubbles are easily generated on the surface of the alloy.
  • a preferred range in the present invention is in the range of 0.1 to 0.5 wt%.
  • a more preferred range is 0.30 to 0.60 wt% or 0.40 to 0.60 wt% or 0.10 to 0.50 wt%.
  • Manganese (Mn) increases the strength of the aluminum alloy.
  • the manganese (Mn) content is less than 0.5wt%, the effect of increasing the strength is small, there is an effect of removing the bad effect of adding iron (Fe) and the effect of refining the grains, and a compound that does not impair corrosion resistance is formed. Therefore, it is possible to improve the strength without lowering the corrosion resistance.
  • an excessive amount of manganese (Mn) may lower the mechanical strength of the aluminum alloy, so care must be taken. In addition, it can cause hot spots in casting, and has the effect of increasing the releasability from the mold.
  • a preferred range in the present invention is 0.0001 to 0.80 wt%, and a more preferred range is 0.30 to 0.60 wt% or 0.0001 to 0.30 wt% or 0.50 to 0.80 wt%.
  • Copper (Cu) is dissolved in the matrix to increase the strength of the aluminum alloy and cause an age hardening effect.
  • the content is less than 0.12wt%, it is difficult to show the effect of adding copper, such as corrosion resistance, and when the content exceeds 0.45wt%, both extrudability and corrosion resistance are reduced at the same time.
  • it exceeds the appropriate amount fluidity will fall.
  • copper (Cu) is more than an appropriate content, precipitates tend to form at grain boundaries, which increases sensitivity to intergranular corrosion and local corrosion, resulting in a side effect of lowering strength. It is known to improve the resistance to stress corrosion cracking in the case of a small addition of 0.15 wt% or less.
  • a preferred range in the present invention is 0.0001 to 0.60 wt%, and a more preferred range is 0.0001 to 0.25 wt% or 0.0001 to 0.60 wt% or 0.0001 to 0.030 wt%.
  • Zinc (Zn) can coexist with magnesium (Mg) to improve mechanical properties and significantly improve castability. It also exhibits some effect on age hardening.
  • a preferred range in the present invention is 0.0001 to 0.50 wt%, and a more preferred range is 0.0001 to 0.25 wt% or 0.0001 to 0.50 wt% or 0.0001 to 0.10 wt%.
  • Iron (Fe) is an element that precipitates as an intermetallic compound in an aluminum alloy and improves wear resistance. If the content is less than 0.1wt%, there is almost no wear resistance effect, and if it exceeds 0.3wt%, the particles are coarsened and workability is deteriorated.
  • an Al 3 Fe compound is formed even in a very small amount, and since it is combined with silicon (Si) to form an Al-Fe-Si intermetallic compound, it is a factor of deterioration of mechanical properties. Even a small amount deteriorates the surface gloss and weakens corrosion resistance and ductility.
  • Iron (Fe) prevents sintering in the mold during the die casting process, and the amount added at this time is sufficient if it is 0.5 wt% to 1.0 wt% or less, and if it exceeds 0.5 wt%, the ductility of the alloy tends to decrease.
  • a preferred range in the present invention is 1.30 wt% or less. A more preferred range is 0.55 wt% or less or 0.15 wt% or less.
  • Titanium (Ti) improves mechanical properties as a particle refining element, and has an effect of preventing cracks. If it is less than 0.05 wt%, there is no effect, and if it is 0.2 wt% or more, a decrease in elongation may occur. When added excessively, there is a problem of causing brittleness, so it is preferable to be added within an appropriate range. When it exceeds 0.25 wt%, a coarse intermetallic compound is formed to reduce formability (processability).
  • a preferred range in the present invention is 0.30 wt% or less.
  • a more preferred range is 0.20 wt% or less or 0.15 wt% or less.
  • Strontium (Sr) improves the flowability by changing the shape of the alloy structure, particularly the AlSi structure, from needle to fine spherical shape.
  • sodium (Na) played such a role, but sodium (Na) has high oxidizing properties and acts to lower the melting point of the alloy, and is being replaced with strontium (Sr) in recent years.
  • strontium (Sr) in recent years.
  • a preferred range in the present invention is 0.0001 to 0.045 wt% or 0.003 to 0.030 or 0.005 to 0.015 wt%.
  • Zirconium (Zr) exhibits precipitation hardening and grain refinement effects. If it is less than 0.05wt%, the crystal grain refinement effect is weak, and if it is more than 0.2wt%, it affects the elongation reduction.
  • a preferred range in the present invention is 0.0001 to 0.30 wt% or 0.05 to 0.30 wt%.
  • Molybdenum (Mo) is dissolved in aluminum grains to increase the strength from 0.05wt% addition. At this time, it is characterized in that the elongation is increased without a decrease in other mechanical properties. However, care must be taken because the addition of Mo increases the melting point of the alloy.
  • a preferred range in the present invention is in the range of 0.0001 to 0.50 wt%.
  • a more preferable range is in the range of 0.05 to 0.50 wt%.
  • the greatest feature of the present invention is that a rare earth metal (RE) having an atomic number of 57 (La) to 71 (Lu) containing cerium (Ce) and lanthanum (La) is added to an aluminum alloy in an appropriate amount to improve strength and It has greatly improved ductility and corrosion resistance and releasability.
  • RE rare earth metal
  • corrosion resistance is strengthened by reducing components such as iron (Fe) and nickel (Ni), which are corrosion-resistant elements present in the molten metal during aluminum production.
  • the rare earth metal since the rare earth metal has an effect of increasing the corrosion potential, it is possible to minimize the addition of copper (Cu) or to replace copper (Cu). Therefore, when the copper (Cu) content is increased to increase the corrosion potential, there is an effect of minimizing these side effects, and thus the corrosion resistance is improved.
  • the lifetime of the oxide film is extended and corrosion resistance is improved.
  • the plastic workability of the metal is improved, and there is an effect of improving the brazing properties.
  • rare earth metals increase the surface gloss by changing the alloy surface properties and increase the mold releasability.
  • the application field of the aluminum alloy can be expanded by adding a rare earth metal to improve corrosion resistance and releasability, which are disadvantages of the aluminum alloy for high-strength, high-toughness casting.
  • the preferred range is 0.0001 to 3.0 wt%, and more preferably, the content range of cerium (Ce), lanthanum (La), other rare earths, or a combination thereof is 0.05 to 1.5 wt%.
  • the aluminum alloy is an alloying element widely used in the aluminum industry (Cr, V, Ni, In, Pb, Bi, Ca, Na, P, B, Ag, Pd, Sb, Sc, Nb, Co, Mo, Be, Hf or Y) and unavoidable impurities may be further included.
  • phosphorus when the phosphorus component in the form of gallium phosphide or indium phosphide is added in the range of 1 to 250 ppm or 1 to 30 ppm, there is a grain refining effect, and in the case of boron (B), the grain refining effect is also effective.
  • the alloying element zirconium (Zr) may be added in the form of a metal, but may be present in the alloy in the form of a nanoparticle-sized oxide to further enhance the effect of the addition. This is one of the great features of the present invention.
  • the nano-sized particles of zirconium oxide are finely distributed in the aluminum alloy, by the principle of fine particle dispersion strengthening, the movement of dislocations that appear during the deformation of the alloy within the grains is prevented, so that the strength can be improved without reducing the ductility.
  • zirconium (Zr) is added to the alloy as a metal component, the ductility is reduced above a certain concentration, but when it is finely dispersed and distributed in the form of nano-particle oxides, the ductility does not decrease even at a certain amount or more, unlike the metal component. There are features that do not.
  • Zirconium has a melting point of 1,855° C. and is difficult to dissolve in a general aluminum alloy manufacturing process. At this time, zirconium is present as a metal component in the alloy.
  • zirconium (Zr) in the form of a fine oxide in the alloy, either a nanometer-sized zirconium oxide fine powder such as ZrO 2 is added to the aluminum molten metal, or ZrH, ZrH 2 , ZrH 4 In the form of a zirconium hydride powder such as ZrH 4 It can be put into aluminum molten metal. However, since it is difficult to obtain a uniform dispersion state in the method of directly inputting the molten metal, it is more efficient to prepare the Al-ZrO 2 master alloy and then inject the master alloy into the molten metal.
  • the particles When preparing the master alloy, it is preferable to divide the particles into several batches and add them in small amounts so that they can be uniformly dispersed in the master alloy. Similarly SiO 2 , Al 2 O 3 , Y 2 O 3 , CeO 2 , La 2 O 3 The addition of nano-sized particles such as ZrO 2 can produce a similar effect. At this time, the preferred range of the oxide (ZrO 2 , SiO 2 , Al 2 O 3 , Y 2 O 3 , CeO 2 , La 2 O 3 ) is in the range of 0.0001 to 0.50 wt%.
  • Molybdenum (Mo) has a high melting point, so it is preferable to use an Al-Mo master alloy when added to the molten metal.
  • the aluminum alloy is rapidly cooled after solution heat treatment at 350 to 550° C. for 1 hour to 10 hours, and then subjected to aging heat treatment at 100 to 200° C. for 1 hour to 10 hours to further strengthen the properties of the alloy. can do it
  • the temperature of the molten alloy was controlled in a temperature range of 670 to 850° C. using a crucible electric furnace, and an ingot was manufactured through casting. This ingot was mold-cast through a die-casting device, and a typical range used in aluminum die-casting was used for the process parameters at this time. T6 heat treatment was performed under normal heat treatment conditions.
  • the alloy compositions and heat treatment conditions of Comparative Examples and Examples of the present invention are shown in Table 2.
  • a tensile test was performed according to KS standards. It was carried out according to the test method.
  • SWAAT evaluation was performed according to the ASTM standard, and the results are shown in Table 3.
  • the SWAAT evaluation was performed according to ASTM standard G85.
  • the evaluation of releasability after die casting was evaluated in 5 steps from A (best) to E (lowest) by visually checking the degree of bubble formation, pinhole formation, and wrinkle formation after the casting was removed from the mold after casting.
  • Comparative Example and Example 3 of the present invention show that although the conditions are similar, the case of the present invention is superior.
  • the addition of Sr and Zr shows the effect of increasing the tensile strength
  • the addition of the rare earth shows the improvement of ductility, corrosion resistance and releasability.
  • T6 heat treatment increases tensile strength and yield strength, but decreases ductility somewhat.
  • the metal zirconium is replaced with zirconium oxide, it can be seen that the ductility is improved while minimizing the decrease in strength. This trend can also be confirmed in FIG. 1 .

Abstract

La présente invention concerne un alliage d'aluminium pour la coulée et son procédé de fabrication et dans une technique de fabrication d'un alliage d'aluminium pour la coulée à ténacité élevée, le silicium (Si), un élément de terre rare et similaire sont ajoutés à un alliage d'aluminium pour améliorer la résistance, la ténacité, la résistance à la corrosion et la capacité de libération tout en maintenant la fluidité d'un alliage pour la coulée. Plus particulièrement, l'invention concerne : un alliage d'aluminium qui est supérieur à des alliages à base d'AC4Aet d'ALDC3, qui sont l'aluminium pour la coulée ; et son procédé de fabrication. L'alliage d'aluminium de la présente invention comprend 8,0 à 11,5 % en poids de silicium (Si), 0,10 à 0,60 % en poids de magnésium (Mg), 0,0001 à 0,80 % en poids de manganèse (Mn), 0,0001 à 0,60 % en poids de cuivre (Cu), 0,0001 à 0,50 % en poids de zinc (Zn), 1,3 % en poids ou moins de fer (Fe), 0,3 % en poids ou moins de titane (Ti) et un élément de terre rare tel que le cérium (Ce) et le lanthane (La).
PCT/KR2020/018860 2020-12-22 2020-12-22 Alliage d'aluminium pour coulée à ténacité élevée et son procédé de fabrication WO2022139007A1 (fr)

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CN115261682A (zh) * 2022-08-12 2022-11-01 苏州大学 铸造铝合金及制备方法
CN115386771A (zh) * 2022-10-27 2022-11-25 广州致远新材料科技有限公司 铝合金材料及其制备方法及道闸传动结构件的压铸方法
CN115418535A (zh) * 2022-08-23 2022-12-02 一汽解放汽车有限公司 铝合金材料及其制备方法和应用、铝合金制品
CN115505799A (zh) * 2022-09-23 2022-12-23 重庆慧鼎华创信息科技有限公司 一种高强韧重力铸造铝合金及其制备方法和应用
CN116240432A (zh) * 2023-02-08 2023-06-09 上海交通大学 一种免热处理压铸铝合金、制备方法及应用
CN117778827A (zh) * 2024-02-22 2024-03-29 鸿劲新材料研究(南通)有限公司 一种新型耐高温发动机缸盖铝合金及其制备方法

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JPH05156398A (ja) * 1991-12-06 1993-06-22 Nippon Light Metal Co Ltd 耐食性に優れた鋳造用アルミニウム合金
WO2016027550A1 (fr) * 2014-08-19 2016-02-25 株式会社オートネットワーク技術研究所 Procédé pour la production de fil d'aluminium
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Publication number Priority date Publication date Assignee Title
CN115261682A (zh) * 2022-08-12 2022-11-01 苏州大学 铸造铝合金及制备方法
CN115418535A (zh) * 2022-08-23 2022-12-02 一汽解放汽车有限公司 铝合金材料及其制备方法和应用、铝合金制品
CN115505799A (zh) * 2022-09-23 2022-12-23 重庆慧鼎华创信息科技有限公司 一种高强韧重力铸造铝合金及其制备方法和应用
CN115386771A (zh) * 2022-10-27 2022-11-25 广州致远新材料科技有限公司 铝合金材料及其制备方法及道闸传动结构件的压铸方法
CN116240432A (zh) * 2023-02-08 2023-06-09 上海交通大学 一种免热处理压铸铝合金、制备方法及应用
CN117778827A (zh) * 2024-02-22 2024-03-29 鸿劲新材料研究(南通)有限公司 一种新型耐高温发动机缸盖铝合金及其制备方法

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