KR101684300B1 - Method of the magnesium alloy castings produced using the calcium silicon alloy powder - Google Patents

Method of the magnesium alloy castings produced using the calcium silicon alloy powder Download PDF

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KR101684300B1
KR101684300B1 KR1020150072961A KR20150072961A KR101684300B1 KR 101684300 B1 KR101684300 B1 KR 101684300B1 KR 1020150072961 A KR1020150072961 A KR 1020150072961A KR 20150072961 A KR20150072961 A KR 20150072961A KR 101684300 B1 KR101684300 B1 KR 101684300B1
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weight
silicon
calcium
magnesium alloy
magnesium
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KR1020150072961A
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Korean (ko)
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KR20160138736A (en
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허일
이동근
이정목
김성국
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주식회사 에스제이테크
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04Casting aluminium or magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting

Abstract

The present invention relates to a method for producing a magnesium alloy casting, comprising: (A) 5.0 to 15.0 wt% aluminum (Al), 0.001 to 3.0 wt% copper, 0.001 to 5.0 wt% silicon, (Ni), 0.002 to 2.0 wt% of iron (Fe), 0.01 to 2.0 wt% of manganese (Mn), and more than 0 wt% to 1.0 wt% of nickel (Ni) Preparing a raw material composed of magnesium (Mg); (B) charging the prepared raw material into a crucible and melting at a temperature of 600 to 800 캜 in a protective gas atmosphere; (C) 0.001 to 30% by weight of calcium silicon (CaSi) composed of 28 to 32% by weight of calcium (Ca) and 55 to 63% by weight of silicon (Si) and 0.001 to 20.0% by weight of yttrium (Y) in powder form; (D) stirring the raw material and the powder so that the mixture is evenly mixed, and stirring the mixed mixture for 300 minutes or less to complete the magnesium alloy melt; And (E) molding the casting by injecting the completed molten metal into the mold while maintaining the temperature at 600 to 750 ° C.
Accordingly, the present invention has the effect of simultaneously securing eco-friendliness, high rigidity, and mechanical properties that can eliminate the use of beryllium (Be) and sulfur hexafluoride (SF 6 ) gases which are harmful substances.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a magnesium alloy casting using calcium silicon alloy powder,

The present invention relates to a process for preparing a magnesium alloy casting, more specifically, to increase the ignition temperature of the magnesium suppress ignition and while preventing the oxidation of global warming substance, sulfur hexafluoride (SF 6) preclude the use of gas Eco And a process for producing a magnesium alloy casting product using the calcium silicon alloy powder having both high strength and nonflammability.

In general, magnesium alloys are lightest alloys with high specific strength and can be applied to various casting and machining processes. They can be applied to all fields requiring light weight, such as automobile parts and electromagnetic parts, and their application range is very wide. However, the magnesium alloy is electrochemically low in electric potential and is a highly active metal. It shows a strong active reaction when it comes into contact with oxygen or water. In the case of commercial alloy, the ignition temperature does not exceed 550 ° C in most cases, On the side, it is still insufficient. That is, the range of application is limited as compared with the potential of the magnesium alloy, and there is a problem that it can not be used in fields requiring safety.

Above all, due to the activation reaction of the magnesium alloy, there is a condition in which an inert atmosphere is required to be formed by using a flux or a mixed gas such as carbon dioxide (CO 2 ) + sulfur hexafluoride (SF 6 ). Here, since the flux is chlorinated, if the conditions for the molten metal are not met, there is a problem that the residual chlorine remains in the material and the corrosion resistance is greatly deteriorated. Therefore, in order to solve such a problem, a method of dissolving and casting in an atmosphere in which carbon dioxide, sulfur hexafluoride and air were mixed instead of flux was effectively proposed. However, sulfur hexafluoride is classified as 23,900 times the global warming potential of carbon dioxide and is expected to be regulated for future use.

To solve these problems, studies have been made to improve the ignition temperature of a magnesium alloy by adding rare earth metals such as calcium (Ca) and beryllium (Be) in order to improve the oxidation resistance of the magnesium alloy itself. However, when calcium is added in an amount exceeding 2.0% by weight, the tensile properties of the magnesium alloy are generally lowered, and particularly, a decrease in elongation is remarkable, so that a large amount of coarse hard phase is formed and cracks are generated. On the other hand, when 3.0 wt% or more of beryllium is added, the resistance to ignition can be improved while the ductility is not significantly lowered. However, the cost competitiveness is lowered due to the high cost, and the substances that regulate the use of electronic products . There is a need for the development of a magnesium alloy that simultaneously satisfies ignition resistance and tensile properties.

For example, Korean Patent Registration No. 10-1066536 entitled " Flammable Magnesium Alloy with Excellent Mechanical Properties and Its Manufacturing Method ", and Korean Patent Registration No. 10-1258470 "High Strength High Flammability Magnesium Alloy" The developed magnesium alloy improves the ignition resistance of the magnesium alloy by adding calcium (Ca) to form a thin and dense calcium oxide layer (CaO) on the surface of the molten metal to suppress oxidation of the molten metal. And Al 2 Y sikimyeo particles are formed to improve the tensile properties layer on the molten metal surface (Y 2 O 3) to form box and magnesium (MgO) and calcium oxide with that by the addition of yttrium (Y) refine the crystal grains of the cast material ( CaO) and mixed layer to increase ignition resistance.

However, when calcium (Ca) is added to the magnesium melt, it is decomposed after forming only the calcium oxide (CaO) layer. Therefore, when the addition amount of calcium is increased to improve the resistance to ignition, And the mechanical properties are rapidly deteriorated. Therefore, it is still difficult to commercialize them.

Korean Patent Registration No. 10-1066536 "Flame-retardant magnesium alloy having excellent mechanical properties and method for producing the same" Korean Patent Registration No. 10-1258470 "High Strength High Flammability Magnesium Alloy"

Accordingly, it is an object of the present invention to fundamentally solve the conventional problems as described above, and it is an object of the present invention to eliminate the use of harmful beryllium (Be) and sulfur hexafluoride (SF 6 ) gases, The present invention also provides a method of manufacturing a magnesium alloy casting product using the calcium silicon alloy powder capable of simultaneously improving the characteristics of the magnesium alloy casting.

In order to achieve the above object, the present invention provides a method for producing a magnesium alloy casting product, comprising the steps of: (A) mixing 5.0 to 15.0 wt% aluminum, 0.001 to 3.0 wt% copper, 0.001 to 5.0 wt% (Si), 0.1 to 9.0 wt% of zinc, 0.002 to 2.0 wt% of iron, 0.01 to 2.0 wt% of manganese (Mn), and 0 to 1.0 wt% of nickel Ni) and magnesium (Mg) as a remainder; (B) charging the prepared raw material into a crucible and melting at a temperature of 600 to 800 캜 in a protective gas atmosphere; (C) 0.001 to 30% by weight of calcium silicon (CaSi) composed of 28 to 32% by weight of calcium (Ca) and 55 to 63% by weight of silicon (Si) and 0.001 to 20.0% by weight of yttrium (Y) in powder form; (D) stirring the raw material and the powder so that the mixture is evenly mixed, and stirring the mixed mixture for 300 minutes or less to complete the magnesium alloy melt; And (E) molding the casting by injecting the finished molten metal into the mold while maintaining the temperature at 600 to 750 ° C.

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It should be understood, however, that the terminology or words of the present specification and claims should not be construed in an ordinary sense or in a dictionary, and that the inventors shall not be limited to the concept of a term It should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be properly defined. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It is to be understood that equivalents and modifications are possible.

As described above, the present invention can eliminate the use of beryllium (Be) and sulfur hexafluoride (SF 6 ) gases which are harmful substances in the melting and casting process by adding calcium silicon (CaSi) (Mg 2 Si) particles are formed on the crystal grains of the alloy to improve the high stiffness and mechanical properties, and thus it can be applied to various machines and electronic parts. As a result, There is an effect that it can be achieved.

Hereinafter, preferred embodiments according to the present invention will be described in detail.

One aspect of the present invention relates to a magnesium alloy, which comprises aluminum (Al), copper (Cu), silicon (Si), zinc (Zn), iron (Fe), and the like, so as to have excellent castability and mechanical properties, Magnesium alloy for die casting which is composed of manganese (Mn), calcium silicon (CaSi), yttrium (Y), nickel (Ni) and magnesium (Mg) and the remaining unavoidable impurities.

Aluminum (Al) -

Aluminum serves to increase the strength of the alloy and improve fluidity and castability. Such aluminum is preferably included in the range of 5.0 to 15.0% based on the total weight of the alloy. That is, when the aluminum content is 15% or more, the tensile properties are deteriorated. When the aluminum content is 5.0% or less, the flowability and castability can not be improved.

- Copper (Cu) -

Copper plays a role in improving the strength of the alloy due to the hardening effect. It is preferable that such copper is included in the range of 0.001 to 3.0% based on the total weight of the alloy. That is, when the copper content is less than 0.001%, the effect of improving the strength is deteriorated. When the copper content is 3.0% or more, the corrosion resistance is deteriorated.

- Silicon (Si) -

Silicon forms calcium magnesium silicate (Mg 2 Si) grains in the crystal grains of the alloy together with calcium silicon (CaSi), thereby increasing the overall strength of the alloy. Such silicon is preferably included in the range of 0.001 to 5.0% based on the total weight of the alloy. That is, when silicon is 5.0% or more, magnesium silicate is excessively generated and brittleness becomes worse, and when it is 0.001% or less, crack prevention and fluidity can not be secured.

- iron (Fe) -

Iron plays a role in preventing sticking in molds. Such iron is preferably included in the range of 0.01 to 2.0% based on the total weight of the alloy. That is, when the iron content is 2.0% or more, the corrosion resistance is lowered and the further improvement of the adhesion is not achieved. If the iron content is less than 0.01, the adhesion can not be prevented.

- manganese (Mn) -

Manganese improves corrosion resistance by bonding with harmful harmful impurities in alloys, and improves strength at fast cooling rate. Such manganese is preferably contained in an amount of 0.01 to 2.0% based on the total weight of the alloy. That is, when manganese is 2.0% or more, the mechanical properties are deteriorated. When the manganese is 0.01 or less, corrosion resistance and strength can not be improved.

- Nickel (Ni) -

Nickel is a hazardous element that is prohibited to use, but it plays a role in improving the corrosion of the alloy. Therefore, it can be selectively included according to the characteristics of the casting. When adding such nickel, it is preferable to add 1.0% or less based on the total weight of the alloy. That is, even if 1.0% or more of nickel is added, corrosion resistance is not remarkably improved.

- calcium silicon (CaSi) -

Calcium silicon plays a role in enhancing the high rigidity and mechanical properties of the overall alloy, while eliminating the use of harmful beryllium (Be) and sulfur hexafluoride (SF 6 ) gases. The calcium silicon is preferably selected from the group consisting of 28-32 wt% calcium (Ca), 55-63 wt% silicon (Si), the balance iron (Fe), aluminum (Al), titanium (Ti) P), and sulfur (S), which may be in the form of masses or particles, but powdery form is preferable in order to promote the reaction in the melt. When calcium silicon is added, a dense calcium oxide (CaO) layer is formed on the surface of the molten metal, and silicon (Si) reacts with magnesium (Mg) to form fine magnesium silicide (Mg 2 Si) It does. It is preferable to add calcium silicon in an amount of 0.001 to 30.0% by weight based on the total weight of the alloy. If the added amount of calcium silicon exceeds 30% by weight, the main composition of the molten metal decreases and the stickiness with the mold increases.

- Yttrium (Y) -

Yttrium plays a role in improving creep in high temperature and refining the crystal grains of the alloy. That is, when yttrium is added, a yttrium oxide (Y 2 O 3 ) layer is formed to improve the ignition resistance, and Al 2 Y particles are formed in the crystal grains of the alloy to improve phosphor properties. Yttrium is preferably added in an amount of 0.001 to 20.0% based on the total weight of the alloy. If the added amount of yttrium is 20% or more, the price of the alloy is increased and the grain of the Al 2 Y particles is lost to refine grains.

Another aspect of the present invention is a method of manufacturing a cast article using the magnesium alloy. (Al), 0.001 to 3.0 wt% copper, 0.001 to 5.0 wt% silicon (Si), 0.1 to 9.0 wt% zinc (Zn), 0.002 to 2.0 wt% (A) preparing a raw material composed of at least one of iron (Fe), 0.01 to 2.0 wt% of manganese (Mn), and more than 0 to 1.0 wt% of nickel (Ni) and magnesium ≪ / RTI > Then, the raw material prepared in the step (A) is charged into the crucible and the step (B) is carried out in a protective gas atmosphere at a temperature of 600 to 800 ° C.

And then (C) adding 0.001 to 30% by weight of calcium silicon (CaSi) and 0.001 to 20.0% by weight of yttrium (Y) to the raw material dissolved in step (B). Then, the raw material and the powder are firstly mixed so as to be evenly mixed, and the mixed mixture is agitated for 300 minutes or less to complete the magnesium alloy melt (D). Finally, a step (E) is performed in which the molten metal obtained in the step (D) is injected into the mold while maintaining the temperature at 600 to 750 ° C. to mold the casting. Here, calcium silicon (CaSi) and yttrium (Y) are preferably added in powder form to promote the reaction with the molten metal.

The finished castings have both high strength and nonflammability, but also excellent mechanical properties. That is, it has a tensile strength of 228 to 230 MPa, a yield strength of 160 to 180 MPa, and a fracture elongation of 3.0 to 4.5%.

Hereinafter, a specific example of the present invention will be described and it will be understood that the substantial effect of the alloy is effective.

<< Experimental Method >>

An alloy made of the material of the present invention and an alloy composed of a conventional material were respectively prepared as ASTM Subsize standard tensile test specimens respectively as Example 1 and Example 2 and Comparative Example, and then subjected to tensile test using an universal material testing machine (Instron 5982) I measured the test. Tensile strength, yield strength and fracture rupture ratio according to Examples and Comparative Examples were measured by tensile test.

<Sample Preparation>

division Al Zr Si Zn Fe Mn Ca Y Ni Mg Comparative Example 3.0 0.6 0.04 3.0 0.004 0.5 1.0 1.0 0.001 Remainder

Unit: wt%

division Al Cu Si Zn Fe Mn CaSi Y Ni Mg Example 1 7.5 0.001 3 4.5 0.1 1.2 15 15 0.5 Remainder Example 2 7.5 3 3 4.5 0.1 1.2 15 15 0.5 Remainder

Unit: wt%

<Specification of Tensile Specimen>

Figure 112015050190241-pat00001

division Center
Street
(G)
width
(w)
thickness
(T)
Shoulder part
radius
(R)
Specimen
Jong Gil
(L)
Parallel portion
Length
(A)
Bottom
width
(C)
Subsize (Plate) 25 6.25 3.05 6 100
More than
32 10

Unit: mm

<Tensile test: stress-strain diagram (tensile strength, yield strength, elongation)>

Figure 112015050190241-pat00002

<Experimental Results>

division Tensile strength (MPa) Yield strength (MPa) Elongation (%) Comparative Example 191 150 3.1 Example 1 228.91 165 4.17 Example 2 228.59 180 3.48

Experimental Results The examples according to the present invention have a tensile strength of 228 to 230 MPa, a yield strength of 160 to 180 MPa and a fracture elongation of 3.0 to 4.5%, while the conventional comparative examples have a tensile strength of 191 MPa, 3.1% elongation at break.

That is, the comparative example is judged to have lower strength than the embodiment because calcium (Ca) added for the purpose of eliminating noxious gas is decomposed after forming only a calcium oxide (CaO) layer when added to the magnesium melt . However, since calcium silicon (CaSi) is added to the embodiment, silicon (Si) reacts with magnesium ions (Mg 2 ) together with a calcium oxide (CaO) layer to form magnesium silicide (Mg 2 Si) To improve overall stiffness and mechanical properties.

As described above, the present invention can eliminate the use of beryllium (Be) and sulfur hexafluoride (SF 6 ) gases, which are harmful substances, so that an eco-friendly manufacturing process can be established, as well as rigidity and mechanical characteristics can be improved at the same time.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore intended that such variations and modifications fall within the scope of the appended claims.

Claims (4)

A method of making a magnesium alloy casting comprising:
(A) 5.0 to 15.0 wt% Aluminum, 0.001 to 3.0 wt% copper, 0.001 to 5.0 wt% silicon, 0.1 to 9.0 wt% zinc, 0.002 to 2.0 (Ni) and magnesium (Mg) in an amount of more than 0 wt% and not more than 1.0 wt% based on the total amount of iron (Fe), 0.01 to 2.0 wt% of manganese (Mn)
(B) charging the prepared raw material into a crucible and melting at a temperature of 600 to 800 캜 in a protective gas atmosphere;
(C) 0.001 to 30% by weight of calcium silicon (CaSi) composed of 28 to 32% by weight of calcium (Ca) and 55 to 63% by weight of silicon (Si) and 0.001 to 20.0% by weight of yttrium (Y) in powder form;
(D) stirring the raw material and the powder so that the mixture is evenly mixed, and stirring the mixed mixture for 300 minutes or less to complete the magnesium alloy melt; And
(E) injecting the completed molten metal into a mold while maintaining the molten metal at a temperature of 600 to 750 ° C to mold the casting. The method for manufacturing a magnesium alloy casting product according to claim 1,
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111118363A (en) * 2020-01-15 2020-05-08 太原科技大学 High-compression-resistance rapidly-degradable magnesium alloy and preparation method thereof

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CN112458347A (en) * 2020-10-28 2021-03-09 南京国重新金属材料研究院有限公司 Cu-SiCp enhanced magnesium alloy and preparation method thereof

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JPH08134581A (en) * 1994-11-14 1996-05-28 Mitsui Mining & Smelting Co Ltd Production of magnesium alloy
KR101066536B1 (en) 2010-10-05 2011-09-21 한국기계연구원 Ignition-proof magnesium alloy with excellent mechanical properties and method for manufacturing the ignition-proof magnesium alloy
KR101402896B1 (en) * 2011-05-20 2014-06-02 한국생산기술연구원 Aluminium alloy and manufacturing method thereof
KR101258470B1 (en) 2011-07-26 2013-04-26 한국기계연구원 High-Strength High-Ductility Ignition-Proof Magnesium Alloy

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111118363A (en) * 2020-01-15 2020-05-08 太原科技大学 High-compression-resistance rapidly-degradable magnesium alloy and preparation method thereof

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