WO2008133218A1 - Alliage de magnésium pour la coulée et pièce coulée d'alliage de magnésium - Google Patents

Alliage de magnésium pour la coulée et pièce coulée d'alliage de magnésium Download PDF

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Publication number
WO2008133218A1
WO2008133218A1 PCT/JP2008/057646 JP2008057646W WO2008133218A1 WO 2008133218 A1 WO2008133218 A1 WO 2008133218A1 JP 2008057646 W JP2008057646 W JP 2008057646W WO 2008133218 A1 WO2008133218 A1 WO 2008133218A1
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WIPO (PCT)
Prior art keywords
mass
magnesium alloy
compound
magnesium
alloy
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Application number
PCT/JP2008/057646
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English (en)
Japanese (ja)
Inventor
Yuki Okamoto
Kyoichi Kinoshita
Motoharu Tanizawa
Kazuhiko Yoshida
Original Assignee
Kabushiki Kaisha Toyota Jidoshokki
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.)
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Application filed by Kabushiki Kaisha Toyota Jidoshokki filed Critical Kabushiki Kaisha Toyota Jidoshokki
Priority to US12/596,815 priority Critical patent/US20100209285A1/en
Priority to EP08740692A priority patent/EP2138595A1/fr
Publication of WO2008133218A1 publication Critical patent/WO2008133218A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium

Definitions

  • the present invention relates to a magnesium alloy for fabrication suitable for use at high temperatures.
  • Magnesium alloys which are lighter than aluminum alloys, are being widely used as aviation vehicle materials and the like from the viewpoint of weight reduction.
  • the magnesium alloy is not sufficient in bowing and heat resistance depending on the application, and therefore further improvement in properties is required.
  • a common magnesium alloy is AZ 91D (ASTM symbol). Since the thermal conductivity of AZ91D is about 73 WZmK, if it is used for a member that is used in a high temperature environment or generates heat during use, heat dissipation may not be performed well, and the member may be thermally deformed. In particular, if a magnesium alloy with a low conductivity is used as the magnesium alloy used for the cylinder head of the inner thigh and the cylinder block, the cylinder head is thermally deformed, the heat is accumulated in the cylinder block and the cylinder bore is deformed. Adverse effects such as increased friction and reduced airtightness occur. For this reason, there is a need for a magnesium alloy that has high heat conductivity and that can perform heat dissipation well and is suitable for use at high temperatures.
  • Mg- 3% Cu- l% "mass 0/0" if thief (units of Ca :).
  • the creep resistance at high temperature is not sufficient depending on the usage conditions.
  • an object of the present invention is to provide a magnesium alloy for forging that is suitable for use at high temperatures. It is also intended to produce a ceramic material made of a magnesium alloy.
  • the present inventors have improved the cleaving resistance at high temperatures without adversely affecting the 3 ⁇ 4i conductivity of the magnesium alloy by adding tin as an alloying element of the magnesium alloy together with copper and strength russium. Based on this, the present inventors have reached the present invention.
  • the total magnesium alloy of the present invention is 100% by mass, 1% by mass to 5% by mass of copper (Cu) and 0.1% by mass or more and 5% by mass or less of canorecium ( (Ca), and a mass ratio (Sn / Ca) from 0.1 to 3 with respect to Ca, and the balance is composed of magnesium (Mg) and inevitable impurities.
  • Cu copper
  • Ca canorecium
  • Sn / Ca mass ratio
  • the magnesium alloy for forging of the present invention contains Cu, Ca, and Sn, so that a crystallized product of Mg—Ca—Sn compound together with Mg—Cu compound is network-like (at the grain boundary of Mg crystal grains). Crystallizes in a three-dimensional network.
  • the three-dimensional network structure suppresses intergranular slip, which becomes particularly active at high temperatures, and improves high-temperature strength and creep resistance at high temperatures.
  • Mg—Ca—S compounds are relatively brittle, but Mg—Ca—Sn compounds in which part of C— of Mg—Ca compounds is replaced with Sn have high strength.
  • 3 daughters of magnesium alloy improve.
  • Sn forms a compound preferentially with Ca, so it has less influence on conductivity than other additive elements such as aluminum.
  • X—Y compound or the like is, for example, a compound having X and ⁇ as shown by ⁇ 2 ⁇ in the composition formula.
  • the magnesium alloy product of the present invention is a magnesium alloy for use in the present invention. This is a fake.
  • the magnesium alloy porcelain of the present invention is
  • Fig. 1 is a graph showing the thermal conductivity of magnesium alloys with different alloy yarns.
  • Fig. 2 is a graph showing the amount of stress reduction 40 hours after the start of the test in the stress relaxation test of magnesium alloys with different alloy compositions.
  • Figure 3 is a graph plotting the compressive stress applied to the specimen every 10 minutes against the test time for stress relaxation difficulty.
  • FIG. 4A and FIG. 4B are photographs in place of drawings showing the metal «of Mg-3 mass% Cu-1 mass 0 / oCa alloy (# 01).
  • FIG. 5A and FIG. 5B are photographs in place of drawings showing the metal structure of the Mg-3 mass 0 / oCu-1 mass 0 / o Ca-0. 1 mass 0 / oS n (# 02) alloy.
  • Fig. 6 A and Fig. 6 B are Mg-3 mass% Cu 1 mass% Ca-1 mass% Sn
  • (# 0 3) is a drawing-substituting photograph showing a metal yarn cage of an alloy.
  • FIG. 7A and FIG. 7B are drawings-substituting photographs showing the metal structure of the Mg—3 mass% Cu—1 mass% Ca—2 mass% Sn (# 04) alloy.
  • FIG. 8 A and Fig. 8 B are Mg-3 mass% ⁇ u-1 mass.
  • FIG. 5 is a drawing-substituting photograph showing the metallographic structure of the / 0 Ca—4 mass% Sn (# 05) alloy. BEST MODE FOR CARRYING OUT THE INVENTION
  • the magnesium alloy for forging of the present invention comprises copper (Cu), calcium (C a) and tin (Sn), with the balance being magnesium (Mg) and inevitable impurities.
  • the crystallized product of Mg—Ca—Sn compound as well as Mg—Cu—S compound can be obtained. It crystallizes in a network (three-dimensional network) at the grain boundaries of Mg grains. Because it is a network with few discontinuous parts, it has a high effect of suppressing grain boundary sliding.
  • the Cu content is 1% by mass or more and 5% by mass when the total magnesium alloy is 100% by mass. /. It is as follows. If the Cu content is 1% by mass or more, Mg-Cu compounds will crystallize sufficiently at the grain boundaries. The Cu content is 1 mass. If it is less than 0 , the strength of the Mg-Cu compound is low due to insufficient crystallization at the grain boundaries. The preferred Cu content is 2% by mass or more. On the other hand, as the amount of Cu increases, the amount of Mg-Cu compound that crystallizes at the crystal grain boundary becomes excessive, resulting in a brittle paper weave. The preferred Cu content is 4 mass. /. It is as follows.
  • the magnesium alloy for forging of the present invention contains Ca and Sn together with Cu.
  • Ca and Sn, together with Cu, contribute to the formation of a three-dimensional network structure as a grain boundary.
  • the Mg-Ca-Sn compound and the Mg-Cu-Sn compound crystallize at the grain boundary, and a good three-dimensional network structure is formed with few discontinuities.
  • the content of C a, upon the entire 3 ⁇ 4 for magnesium alloy is 100 mass 0/0, not more than 1 mass% to 5 mass% 0.5. If the content of C a is 0.1% by mass or more, the Mg—C a—Sn compound is sufficiently crystallized at the grain boundary. In addition, adding Ca to the magnesium alloy increases the ignition of the magnesium alloy, preventing combustion that may occur when the magnesium alloy is made intense. Preferred content of Ca is 0.5 mass. /. That's it. On the other hand, when the Ca content exceeds 5% by mass, the amount of grain boundary crystallized products increases, and mechanical properties such as tensile strength and elongation decrease, resulting in problems in post-processing. is there. A preferable Ca content is 3% by mass or less, and further 2% by mass or less.
  • the Sn content is 0.1 to 3 in terms of mass ratio (Sn / Ca) to calcium (Ca). If the Sn content is 0.1 mass% or more, Mg
  • the -Ca-Sn compound is sufficiently crystallized.
  • the Mg-Ca-Sn compound is divided from the three-dimensional network structure and crystallizes in the crystal grains, making it difficult to form a good three-dimensional network structure. As a result, the creep resistance tends to decrease.
  • ⁇ produces not only Mg—Ca—Sn compounds but also Mg—Sn compounds. Mg-Sn compounds are low melting point compounds, and therefore creep resistance is improved. Therefore, the Sn content is 3 or less with SnZCa. If SnZCa is 3 or less, formation of a low melting point compound is suppressed.
  • SnZCa is 2 or less, a good three-dimensional network structure with little discontinuity is formed, and the high-temperature bow daughter and the creep resistance at high temperature are improved. That is, the preferred Sn content is 311 O &, 2 or less, and 1.5 or less.
  • Sn forms a compound with Ca preferentially over Mg and Cu. Therefore, Cu and Mg-Cu compounds with high thermal conductivity are not adversely affected, and as a result, the conductivity of the magnesium alloy is unlikely to decrease. From this, considering the stoichiometric ratio of SnZCa of MgCa-Sn compounds, the mass ratio of Sn to Ca (Sn / Ca) is 3 or less, or 0.1 or more 2 The following is preferable, and there is almost no Sn that forms a compound with an Mg—Cu compound, and crystallization of the low melting point compound described above is also suppressed.
  • the magnesium alloy for t according to the present invention described above can be used in various fields such as automobiles and electric power as well as space and aviation.
  • a product used under a high temperature environment for example, a compressor, a pump, various cases, etc.
  • Components used and engine parts used under high temperature and high load especially cylinder heads, cylinder blocks and oil vans for internal combustion engines, turbocharger impellers for internal combustion engines, and transmitters used for automobiles, etc. Case.
  • the magnesium alloy ceramic of the present invention is a ceramic made of the magnesium alloy for forging according to the present invention described in detail above. That is, the magnesium alloy case of the present invention is obtained through a pouring step and a solidification step, and the pouring step is 1% by mass or more and 5% by mass when the whole is 100% by mass. / 0 and less copper (Cu), 0.
  • the magnesium alloy of the present invention is not limited to normal gravity pressure fabrication, but may be die cast fabrication.
  • the sand mold, mold, etc. used for dredging can be used.
  • the solidification rate (cooling rate) in the solidification process and the solidification rate to the extent that a three-dimensional network structure is formed can be selected as appropriate according to the size of the clot. If solidified by general solidification, a network-like metal string is obtained.
  • the magnesium alloy and the magnesium compound for use in the present invention are preferably free materials. Furthermore, the characteristics of, may be improved by heat treatment later.
  • the present invention is not limited to the above embodiment.
  • the present invention can be implemented in various forms that have been changed or improved by those skilled in the art without departing from the scope of the present invention.
  • Chloride flux was applied to the inner surface of a crucible preheated in an electric furnace, and a large amount of pure magnesium ingot, pure Cu, and pure Sn as required were dissolved. Furthermore, weighed Ca was added to this molten metal kept at 750 ° C.
  • the agitation was sufficiently stirred to completely dissolve the raw materials, and then kept calm for a while.
  • the various molten alloys obtained in this way were poured into molds of a predetermined shape (the pouring process) and solidified in the atmosphere (solidification process). Forged.
  • the obtained test piece was 30 mm ⁇ 30 mm ⁇ 200 mm.
  • Table 1 shows the chemical composition of each specimen. Measurement of conductivity]
  • test pieces # 01 to # 05 shown in Table 1 were observed. The surface was observed by observing the cross section cut out from each specimen with a metal microscope. The forces shown in Fig. 4A to Fig. 8A and Fig. 4B to Fig. 8B, respectively, on the surface of # 01 to # 05 are shown in Fig. 4A to Fig. 8B. Magnification, Figures 4B-8B (b) The same section was observed at high magnification.
  • test piece # 01 as can be seen from FIG. 4A, a three-dimensional network structure strength formed by crystallization of an intermetallic compound at the grain boundary was obtained.
  • Fig. 4 (b) it is CuMg 2 that appears bright at the grain boundary, and Mg 2 C a that appears bright.
  • # 01 ⁇ The test piece of ⁇ 05 was superior in terms of convection and deviation than A ⁇ 91 D.
  • the thermal conductivity of the # 01 test piece not containing Sn was 155 WZmK, but no decrease in! Rf conductivity due to the addition of Sn was observed in the # 02 to # 04 test pieces.
  • # 05 where the Sn content is excessive although the excellence is superior to A Z 91 D, the difference in the inductivity from # 01 is large.
  • # 02 to # 04 specimens made of magnesium alloy containing Sn had less stress reduction than the specimen # 01 after 40B clearance from the start of wrinkle in the stress relaxation test at 200 ° C. .
  • the addition of Sn to the Mg-Cu-Ca alloy (# 01) improved the creep resistance at high temperatures. This is presumed to be because # 02 to # 04 have a higher 3D network structure than # 01, which has many discontinuous parts in the 3D network structure.
  • 2 masses of Sn. # 04 with / o has better creep resistance after 40 hours than # 01 without Sn, but inferior to # 02 and # 03.
  • the metal structure of # 04 is thought to be because the three-dimensional network structure was incompleter than # 02 and # 03. Contains 4% by mass of Sn # 05, three-dimensional network structure is incomplete, it is contemplated that M g 2 S n which is a low melting compound containing Mutame, creep resistance was Koma ⁇ .
  • # 02 and # 03 pieces had a greater stress drop than # 01 about 3 hours after starting, but the change in stress from 3 to 40 hours was small and stable.
  • # 04 specimen has a greater stress drop than # 01 and A Z9 ID about 3 hours after the start of the test, but the amount of stress change from 3 to 40 hours is small and stable. It was. (Figure 3)
  • each of the above-mentioned pieces has a constant (: 11 is 3% by mass and Ca is 1% by mass.
  • Cu is 2.7%. /. If it is 3 mass% or less, and Ca is 0.7 mass% or more and 1.3 mass% or less, it exhibits the same conductivity and surface creep properties as the above-mentioned pieces.
  • a magnesium alloy containing Cu, Ca and Sn with appropriate contents shows no deterioration in conductivity due to the addition of Sn, and is excellent in creep resistance at high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Forging (AREA)
  • Continuous Casting (AREA)

Abstract

L'invention porte sur un alliage de magnésium de coulée caractérisé par le fait qu'il contient 1-5 % en masse de cuivre (Cu) et 0,1-5 % en masse de calcium (Ca) sur la base de l'alliage total et contenant de l'étain (Sn) dans une quantité telle que le rapport de la masse de Sn à celle du Ca, Sn/Ca, est de 0,1-3, le reste étant le magnésium (Mg) et les impuretés accidentelles. En raison de l'incorporation de Cu, Ca et Sn, des cristaux non seulement du composé Mg-Cu mais d'un composé Mg-Ca-Sn se séparent de façon à former une structure en réseau (structure de réseau tridimensionnelle) à la limite entre des grains de cristaux de Mg. La structure de réseau tridimensionnelle inhibe un glissement aux limites qui est susceptible de se produire notamment aux températures élevées, pour améliorer une résistance à haute température et une résistance au fluage à haute température. Etant donné que le Sn forme un composé de préférence avec le Ca, il exerce moins d'influences défavorables sur la conductivité thermique que les autres éléments additifs.
PCT/JP2008/057646 2007-04-20 2008-04-14 Alliage de magnésium pour la coulée et pièce coulée d'alliage de magnésium WO2008133218A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/596,815 US20100209285A1 (en) 2007-04-20 2008-04-14 Magnesium alloy for casting and magnesium-alloy cast product
EP08740692A EP2138595A1 (fr) 2007-04-20 2008-04-14 Alliage de magnésium pour la coulée et pièce coulée d'alliage de magnésium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-112014 2007-04-20
JP2007112014A JP2008266733A (ja) 2007-04-20 2007-04-20 鋳造用マグネシウム合金およびマグネシウム合金鋳物

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WO2008133218A1 true WO2008133218A1 (fr) 2008-11-06

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EP (1) EP2138595A1 (fr)
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Publication number Priority date Publication date Assignee Title
US8435444B2 (en) 2009-08-26 2013-05-07 Techmag Ag Magnesium alloy
CN103233138B (zh) * 2013-04-28 2015-10-14 重庆大学 Mg-Al系镁合金用晶粒细化剂及其制备方法
KR101573713B1 (ko) * 2013-12-04 2015-12-03 한국생산기술연구원 고열전도도 마그네슘 합금
CN103938045B (zh) * 2014-04-30 2016-04-06 东北大学 一种含钙变形镁合金及其棒材制备方法
CN104561709B (zh) * 2014-12-04 2017-05-17 沈阳工业大学 高蠕变性能铸造镁合金及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5511191A (en) * 1978-05-31 1980-01-25 Magnesium Elektron Ltd Magnesium alloy
JPH0625791A (ja) * 1992-03-25 1994-02-01 Mitsui Mining & Smelting Co Ltd 高強度マグネシウム合金
JP2003113436A (ja) * 2001-10-03 2003-04-18 Matsumoto Seisakusho:Kk 高減衰能マグネシウム合金
JP2005054233A (ja) * 2003-08-04 2005-03-03 Chiba Inst Of Technology 耐熱マグネシウム合金

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5511191A (en) * 1978-05-31 1980-01-25 Magnesium Elektron Ltd Magnesium alloy
JPH0625791A (ja) * 1992-03-25 1994-02-01 Mitsui Mining & Smelting Co Ltd 高強度マグネシウム合金
JP2003113436A (ja) * 2001-10-03 2003-04-18 Matsumoto Seisakusho:Kk 高減衰能マグネシウム合金
JP2005054233A (ja) * 2003-08-04 2005-03-03 Chiba Inst Of Technology 耐熱マグネシウム合金

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAO K.P. ET AL.: "High Temperature Deformation Behaviour of a New Magnesium Alloy", KEY ENGINEERING MATERIALS, vol. 340-341, no. PART 1, 12 April 2007 (2007-04-12), pages 89 - 94 *

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EP2138595A1 (fr) 2009-12-30
US20100209285A1 (en) 2010-08-19

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