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WO2021141169A1 - Alliage de magnésium - Google Patents

Alliage de magnésium Download PDF

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Publication number
WO2021141169A1
WO2021141169A1 PCT/KR2020/000487 KR2020000487W WO2021141169A1 WO 2021141169 A1 WO2021141169 A1 WO 2021141169A1 KR 2020000487 W KR2020000487 W KR 2020000487W WO 2021141169 A1 WO2021141169 A1 WO 2021141169A1
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WO
WIPO (PCT)
Prior art keywords
magnesium alloy
magnesium
calcium
silicon
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2020/000487
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English (en)
Korean (ko)
Inventor
박성현
성면창
김중년
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Electronics Inc
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LG Electronics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Electronics Inc filed Critical LG Electronics Inc
Priority to KR1020227023550A priority Critical patent/KR102844108B1/ko
Priority to PCT/KR2020/000487 priority patent/WO2021141169A1/fr
Publication of WO2021141169A1 publication Critical patent/WO2021141169A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium 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
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • the present invention relates to a magnesium alloy having excellent thermal conductivity.
  • the present invention relates to a magnesium alloy in which thermal conductivity and strength are improved by controlling alloying elements included in the magnesium alloy.
  • the thermal conductivity of pure metals may be higher than that of general alloys.
  • the thermal conductivity of pure magnesium is about 155W/m?K, but as magnesium alloying proceeds, the material added for the alloy interferes with thermal conduction and the thermal conductivity decreases.
  • Al aluminum
  • the present invention is to provide a magnesium alloy having excellent thermal conductivity.
  • the present invention is to provide a magnesium alloy with improved strength while maintaining excellent thermal conductivity.
  • an object of the present invention is to provide a magnesium alloy having good fluidity while maintaining excellent thermal conductivity.
  • the present invention is to provide a magnesium alloy having good hot cracking properties while maintaining excellent thermal conductivity.
  • the present invention is intended to solve all problems that can be generated or predicted from the prior art in addition to the technical problems described above.
  • the magnesium alloy according to the present invention can control the inclusion ratio between alloying elements such as silicon (Si), calcium (Ca), and zinc (Zn).
  • the alloying elements form a crystalline phase, and the weight ratio of silicon, calcium, and zinc satisfies the following condition.
  • the crystalline phase may include at least one of MgCaSi and Mg2Si.
  • the crystalline phase may be included in an amount of 0.1 to 5.5 wt% based on the total weight of the magnesium alloy.
  • the zinc and calcium may further satisfy the following conditions.
  • the remaining part of the alloying element may be dissolved in the magnesium.
  • the dissolved alloy additive element may be 2 wt% or less based on the total weight of the magnesium alloy.
  • the silicon may be in an amount of 0.8 to 1.5 wt% based on the total weight of the magnesium alloy.
  • the silicon is not dissolved, and may be formed in the crystalline phase.
  • the calcium may be 0.64 to 1.8 wt% based on the total weight of the magnesium alloy.
  • At least a portion of the calcium may form the crystalline phase.
  • the zinc may be in an amount of 0.46 to 2.1 wt% based on the total weight of the magnesium alloy.
  • the alloying element may further include aluminum (Al), and the amount of aluminum may be 0.1 to 0.5 wt% based on the total weight of the magnesium alloy.
  • the alloying element may further include manganese (Mn), and the manganese may be 0.1 to 0.5 wt% based on the total weight of the magnesium alloy.
  • the magnesium alloy of the present invention may realize excellent thermal conductivity properties by controlling the inclusion ratio of silicon and calcium to enhance strength and at the same time allowing the alloying elements to exist in a crystalline state.
  • the magnesium alloy of the present invention can improve castability and hot cracking properties while maintaining excellent thermal conductivity by controlling the proportion of alloying elements including silicon, calcium, and zinc.
  • 1 is an EBSD phase map of a commercial magnesium alloy and a magnesium alloy according to the present invention.
  • FIG. 2 is an electron microscope (SEM) photograph showing a Si crystal phase of a magnesium alloy according to an embodiment of the present invention.
  • the magnesium (Mg) alloy according to the embodiment of the present invention improves strength by controlling the proportion of alloying elements including silicon (Si), calcium (Ca) and zinc (Zn), and the alloying element is present in a crystalline state. By doing so, it can have excellent heat conduction properties.
  • thermal conduction of the magnesium alloy may be implemented as the movement of electrons contained in the magnesium alloy. Therefore, the better the electrons move, the better the thermal conductivity of the magnesium alloy.
  • a part of the alloying element included in the magnesium alloy may be dissolved in magnesium, and the remaining part may be combined with magnesium in a predetermined ratio to form a crystalline phase.
  • the substituted alloying element acts as an obstacle blocking the path of electrons that transfer heat within the magnesium alloy, and as a kind of resistor, may lower the thermal conductivity of the magnesium alloy.
  • the alloying element not dissolved in magnesium may have a crystalline state in which it is combined with magnesium in a predetermined ratio.
  • the alloying element forming the crystal phase is locally concentrated within the grain boundary of the crystal phase unlike the case where it is dissolved in magnesium, it acts only as a very small amount of resistance in the movement of electrons.
  • the magnesium alloy according to the embodiment of the present invention controls the type of alloying element and the inclusion ratio between the alloying elements so that a relatively large number of crystalline phases are formed in the magnesium alloy instead of a material having high solid solubility, thereby effectively thermal conductivity characteristics. can improve
  • the crystalline state is a concept distinct from that in which the alloying element is dissolved in magnesium. It is a compound state formed by combining magnesium and the alloying element in a certain ratio to have a new arrangement structure and atomic ratio, and has its own particle size ( It can be distinguished from dissolved magnesium by the grain boundary).
  • the magnesium alloy according to the embodiment of the present invention may include an alloying element including silicon (Si), calcium (Ca), and zinc (Zn).
  • Silicon as an alloying element may be about 0.8 wt% to about 1.5 wt% based on the total weight of the magnesium alloy, and more preferably, about 1.0 wt% to about 1.3 wt%.
  • magnesium alloy contains silicon in the above range, excellent castability (fluidity) can be effectively implemented without degrading thermal conductivity properties.
  • silicon has a latent period of solidification of 50.21 kJ/mol, which is very large compared to the latent heat of solidification of magnesium at 8.48 kJ/mol, so that the magnesium alloy contains silicon, so that the molten metal flowability is improved and castability can be improved.
  • the amount of silicon contained in the magnesium alloy is less than 0.8% by weight, the flowability of the molten metal of the magnesium alloy is lowered, so that sufficient castability cannot be implemented. If the silicon included in the magnesium alloy is more than 1.5 wt%, the melting point of the magnesium alloy is too high, so it may be difficult to use it as an actual die casting melting furnace.
  • Silicon is not dissolved in magnesium at room temperature and may form a magnesium-silicon crystal phase (Mg2Si) and a magnesium-calcium-silicon crystal phase (MgCaSi). Details of the crystal phase formation will be described later.
  • Calcium as an alloying element may be about 0.64 wt% to about 1.8 wt%, more preferably about 0.9 to about 1.43 wt%, based on the total weight of the magnesium alloy.
  • the magnesium alloy contains calcium in the above range, it is possible to prevent oxidation by forming calcium oxide (CaO), and to increase ignition resistance.
  • CaO calcium oxide
  • Calcium may be included in the magnesium alloy while maintaining a constant inclusion ratio by being organically related to zinc and silicon in the above range, which will be described in detail later.
  • Calcium may form a magnesium-calcium-silicon crystalline phase (MgCaSi) with a part of calcium dissolved in magnesium at room temperature, and the remainder with silicon.
  • MgCaSi magnesium-calcium-silicon crystalline phase
  • zinc may be present in an amount of about 0.46 wt% to about 2.43 wt%, more preferably, about 0.65 wt% to about 2.1 wt%, based on the total weight of the magnesium alloy.
  • the magnesium alloy contains zinc in the above range, it is possible to effectively enhance the strength of the magnesium alloy.
  • Zinc is organically related to calcium in the above range and may be included in the magnesium alloy while maintaining a constant inclusion ratio, which will be described in detail later.
  • the magnesium alloy according to the embodiment of the present invention may further include aluminum (Al) and/or manganese (Mn) as alloying elements to improve strength and castability.
  • aluminum and manganese may be about 0.1 to about 0.5 wt% based on the total weight of the magnesium alloy.
  • the magnesium alloy includes aluminum and/or manganese in the above range, it is possible to realize excellent castability and minimize deterioration of thermal conductivity properties due to solid solution.
  • the magnesium alloy according to the embodiment of the present invention may realize excellent heat conduction properties and improve castability and hot cracking properties by controlling the type and ratio of elements included as alloying elements. Hereinafter, it will be described in detail with reference to FIGS. 1 and 3 .
  • the present invention by controlling the inclusion ratio between silicon and calcium, it is possible to induce the formation of a crystalline phase in the magnesium alloy of an element that degrades thermal conductivity and minimize the solid solubility in magnesium.
  • magnesium alloy according to the embodiment of the present invention, calcium is combined with silicon and magnesium to form a crystalline phase, so that calcium is dissolved in magnesium to reduce thermal conductivity degradation.
  • the magnesium alloy according to the embodiment of the present invention may contain less than about 2 wt% of an alloying element dissolved in solid solution based on the total weight, and at the same time maintain a crystal phase of about 0.1 to 4 wt%.
  • the crystalline phase included in the magnesium alloy is included in an amount of the above range by weight, it is possible to effectively reduce the solid solution of the mixed additive element into magnesium, thereby preventing deterioration of thermal conductivity properties.
  • FIG. 1 is a commercial magnesium alloy containing a large amount of aluminum, AZ91 (FIG. 1(a)) and a high thermal conductivity magnesium alloy containing 1.1 wt% of silicon, 0.8 wt% of zinc, and 0.9 wt% of calcium as alloying elements according to the present invention.
  • AZ91 FIG. 1(a)
  • EBSD Electron Back Scattered Diffraction
  • Mg1.95Al0.05 a solid solution phase in which aluminum is dissolved in magnesium.
  • Mg17Al12 crystal phases which are intermetallic compounds of magnesium and aluminum, are formed in several places at the grain boundary and inside the grain.
  • the aluminum element in the form of a solid solution in the magnesium is uniformly dissolved and dissolved in the magnesium, it acts as a kind of resistance when the free electrons of the magnesium metal move and acts as an element to reduce heat conduction.
  • the magnesium alloy according to the embodiment of the present invention has a different characteristic from the microstructure of such a commercial alloy.
  • 1 (b) and 2 are for the crystal phase structure of the high thermal conductivity magnesium alloy according to the embodiment of the present invention.
  • the magnesium alloy according to the present invention has a pure magnesium single phase distributed throughout.
  • magnesium-silicon and calcium which are main additive elements, are not dissolved in magnesium, but combine with magnesium to form magnesium-silicon (Mg-Si) and magnesium-calcium-silicon (MgCaSi) crystal phases.
  • silicon forms Mg2Si and MgCaSi phases, and is distributed as a crystalline phase different from magnesium in grain boundaries and grains in the magnesium alloy.
  • silicon in the magnesium alloy of the embodiment of the present invention does not dissolve in solid solution, and the eutectic phase of acicular magnesium-silicon (Mg-Si) and magnesium-calcium-silicon (MgCaSi) that are plate-shaped or polygonal grains are crystalline. form the primary phase of
  • magnesium-calcium-silicon MgCaSi
  • the magnesium alloy according to the embodiment of the present invention reduces the amount of elements dissolved in magnesium by controlling the inclusion ratio of calcium and silicon, and instead of magnesium-silicon (Mg-Si) and magnesium-calcium-silicon (MgCaSi) crystal phases. designed to form
  • the magnesium alloy of the present invention can realize excellent thermal conductivity by significantly reducing the amount of atoms dissolved in magnesium compared to the conventional commercial magnesium alloy.
  • magnesium-silicon Mg-Si
  • magnesium-calcium-silicon MgCaSi
  • Silicon and calcium included in the magnesium alloy according to the embodiment of the present invention may satisfy a certain weight ratio condition.
  • calcium may be about 0.8 to about 1.2 times silicon weight %.
  • magnesium-calcium-silicon (MgCaSi) crystal phase formed by combining calcium with silicon and magnesium the ratio of calcium to silicon is 1:1.
  • the magnesium alloy according to the embodiment of the present invention maintains the ratio of calcium to silicon at about 0.8 to about 1.2 times close to 1:1.
  • magnesium-calcium-silicon (MgCaSi) phase As a result, most of the added calcium forms a magnesium-calcium-silicon (MgCaSi) phase to reduce the amount of calcium dissolved in magnesium, and the magnesium alloy exhibits excellent thermal conductivity with a thermal conductivity of 120W/m?k or more.
  • the weight % of calcium is less than 0.8 times the weight % of silicon, only a magnesium-silicon (Mg2Si) crystal phase is formed, and the formation of magnesium-calcium-silicon (MgCaSi) is suppressed, and as a result, calcium dissolved in magnesium As the amount of , the thermal conductivity may be deteriorated.
  • Mg2Si magnesium-silicon
  • MgCaSi magnesium-calcium-silicon
  • magnesium-calcium-silicon (MgCaSi) is formed and the remaining calcium is dissolved in magnesium, so that thermal conductivity properties may be deteriorated.
  • FIG. 3 is an observation of the microstructure of the magnesium alloy using an electron microscope (SEM), and FIG. 3 (a) shows that the weight % content ratio of silicon and calcium is 1:0.5, and FIG. 3 (b) shows silicon and calcium.
  • the weight % content ratio of calcium is 1:1.
  • FIG. 3(a) shows that the crystalline phase of magnesium-calcium-silicon (MgCaSi) is not formed because the content of calcium is too small compared to silicon, and magnesium-silicon (Mg-Si) Only a crystalline phase exists, and it can be confirmed that most of the calcium is dissolved in magnesium.
  • MgCaSi magnesium-calcium-silicon
  • calcium and zinc included in the magnesium alloy according to the embodiment of the present invention may satisfy a certain weight ratio condition.
  • calcium may be about 0.6 to about 1.4 times the zinc weight percent.
  • Zinc may be dissolved in a magnesium alloy to improve strength at room temperature as a solid solution strengthening effect without significantly affecting thermal conductivity.
  • the inclusion ratio of zinc in the magnesium alloy is not limited alone, but may be limited by a relative inclusion ratio with calcium.
  • calcium and zinc may be combined in a 2:3 ratio to form a crystal phase of calcium-magnesium-zinc (Ca2Mg6Zn3) together with magnesium.
  • the added calcium forms a magnesium-calcium-silicon (MgCaSi) crystal phase, and there is no remaining calcium dissolved therein, so calcium-magnesium-zinc (Ca2Mg6Zn3) Since a crystalline phase cannot be formed, the solid solution strengthening effect of zinc can be maintained.
  • MgCaSi magnesium-calcium-silicon
  • Ca2Mg6Zn3 calcium-magnesium-zinc
  • the magnesium alloy according to the embodiment of the present invention may contain a sum of calcium and zinc based on the total weight of the magnesium alloy in an amount of about 1.14 to about 3.9 wt%, preferably about 1.14 to about 3.0 wt%.
  • the magnesium alloy according to the embodiment of the present invention can effectively reduce the occurrence of hot cracking properties by controlling the inclusion ratio and amount so that the sum of calcium and zinc is about 1.14 to about 3.9 wt% compared to the magnesium alloy.
  • Examples 1 to 9 are experimental examples in which the respective inclusion ratios and relative inclusion ratios of calcium, silicon, and zinc meet the conditions of the magnesium alloy according to the present invention.
  • Comparative Examples 1 to 16 are experimental examples in which at least one of calcium, silicon, and zinc inclusion ratios and relative inclusion ratios does not meet the magnesium alloy conditions according to the present invention.
  • Table 2 shows the results of measurements of thermal conductivity, molten metal flowability (castability, fluidity), hot cracking properties, and yield strength according to Experimental Examples 1 to 9 and Comparative Examples 1 to 16.
  • thermal conductivity measurement a circular specimen having a diameter of 12.5 mm x 2t was prepared, and then thermal diffusivity was measured using LFA (Laser Flash Analysis) equipment, and then thermal conductivity was obtained.
  • LFA Laser Flash Analysis
  • the composition of each element is a result of measurement using ICP (Inductive Coupled Plasma) spectroscopy.
  • the flowability of hot water is measured by pouring 700 ⁇ C alloy molten metal and using the spiral-test equipment to measure the length of the melt until it solidifies. The longer the flow, the better the flowability.
  • Yield strength was measured using an INSTRON 5967 (standard: ASTM E8) device for the specimen.
  • Comparative Examples 3, 4, 10 and 12 contained less than 0.8 wt % of silicon relative to the total weight of the magnesium alloy, and it could be confirmed that the molten metal flowability was less than 35 cm.
  • Silicon can improve the flowability of the molten metal by including a latent heat of solidification greater than that of magnesium. may not be
  • the silicon content is more than 1.5% based on the total weight of the magnesium alloy, the melting point becomes excessively high, and the castability may also deteriorate.
  • Comparative Examples 9 to 12 showed that the total amount of calcium and zinc was greater than 3.9% by weight, and the hot cracking property exceeded 20 points, so that the thermal cracking properties were excellent. degradation can be seen.

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  • Chemical & Material Sciences (AREA)
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Abstract

Un alliage de magnésium, selon un mode de réalisation de la présente invention, comprend des éléments d'additif d'alliage comprenant du silicium (Si), du calcium (Ca) et du zinc (Zn), au moins une partie des éléments d'additif d'alliage formant une phase cristalline, et le rapport pondéral du silicium au calcium au zinc satisfaisant à la condition suivante : Ca = (0,8 ~ 1,2) * Si (% en poids) Ca = (0,6 ~ 1,4) * Zn (% en poids).
PCT/KR2020/000487 2020-01-10 2020-01-10 Alliage de magnésium Ceased WO2021141169A1 (fr)

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KR1020227023550A KR102844108B1 (ko) 2020-01-10 2020-01-10 마그네슘 합금
PCT/KR2020/000487 WO2021141169A1 (fr) 2020-01-10 2020-01-10 Alliage de magnésium

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PCT/KR2020/000487 WO2021141169A1 (fr) 2020-01-10 2020-01-10 Alliage de magnésium

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WO2021141169A1 true WO2021141169A1 (fr) 2021-07-15

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06330216A (ja) * 1993-05-19 1994-11-29 Nippon Steel Corp マグネシウム合金
KR20190031099A (ko) * 2017-09-15 2019-03-25 엘지전자 주식회사 고열전도 마그네슘 합금 및 이를 이용한 방열 히트 싱크
CN110195178A (zh) * 2018-02-26 2019-09-03 中国宝武钢铁集团有限公司 一种高强高塑性耐热耐燃镁合金及其制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06330216A (ja) * 1993-05-19 1994-11-29 Nippon Steel Corp マグネシウム合金
KR20190031099A (ko) * 2017-09-15 2019-03-25 엘지전자 주식회사 고열전도 마그네슘 합금 및 이를 이용한 방열 히트 싱크
CN110195178A (zh) * 2018-02-26 2019-09-03 中国宝武钢铁集团有限公司 一种高强高塑性耐热耐燃镁合金及其制造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AJITH KUMAR, K. K.; VISWANATH, ABHILASH; PILLAI, U. T. S.; PAI, B. C.; CHAKRABORTY, M.: "Changes in Solidification Morphology of Mg-Si Alloys by Ca Additions", TRANSACTIONS OF THE INDIAN INSTITUTE OF METALS, vol. 65, no. 6, 1 January 2012 (2012-01-01), Transactions of the Indian Institute of Metals ( 2012 ), 65(6),695-699CODEN: TIIMA3; ISSN: 0975-1645, pages 695 - 699, XP009508838, ISSN: 0975-1645, DOI: 10.1007/s12666-012-0212-z *
GIL-SANTOS ANDREA; SZAKACS GABOR; MOELANS NELE; HORT NORBERT; VAN DER BIEST OMER: "Microstructure and mechanical characterization of cast Mg-Ca-Si alloys", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 694, 8 October 2016 (2016-10-08), CH, pages 767 - 776, XP029827228, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2016.10.059 *

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KR102844108B1 (ko) 2025-08-07
KR20220124185A (ko) 2022-09-13

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