EP2692884B1 - Magnesium alloy - Google Patents
Magnesium alloy Download PDFInfo
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- EP2692884B1 EP2692884B1 EP12765196.6A EP12765196A EP2692884B1 EP 2692884 B1 EP2692884 B1 EP 2692884B1 EP 12765196 A EP12765196 A EP 12765196A EP 2692884 B1 EP2692884 B1 EP 2692884B1
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- magnesium alloy
- aluminum
- calcium
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 44
- 239000011575 calcium Substances 0.000 claims description 84
- 229910052782 aluminium Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 41
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 33
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- 229910052712 strontium Inorganic materials 0.000 claims description 31
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 34
- 238000000265 homogenisation Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 29
- 239000000956 alloy Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 229910000765 intermetallic Inorganic materials 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
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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
- C22C23/02—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, particularly a magnesium alloy having high strength and high heat resistance, which can be worked into a wrought material such as an extruded or forged material.
- magnesium is the lightest and has the highest specific strength among practical metals.
- use of a magnesium alloy is expanded in various applications, for example, application of parts which underwent weight reduction using a magnesium alloy.
- parts of the magnesium alloy are formed by a casting or die-casting method.
- Patent Document 1 discloses that a magnesium alloy containing 0.1 to 15% by weight of calcium and optionally containing aluminum or zinc in the amount which does not exceed two times the amount of calcium is subjected to plastic working including extrusion and rolling, thereby homogeneously dispersing a crushed intermetallic compound in crystal grains, thus leading to an enhancement in mechanical strength.
- Patent Document 2 discloses that refining of crystal grains is suppressed by performing hot rolling or forging at a predetermined processing temperature and rolling reduction ratio using a Mg-Al-Ca-Sr-Mn based alloy, and heat resistance is improved by controlling an aspect ratio of crystal grains (length of a major axis of crystal grains/length of a minor axis of crystal grains) without causing drastic fracture of a network intermetallic compound precipitated in the grain boundary.
- Patent Document 3 relates to the problem to provide an Mg-Al-Zn alloy material which has ⁇ 300 MPa tensile strength and uniform mechanical properties and can be easily manufactured by extrusion.
- an Mg-Al-Zn alloy material which includes: (1) a high strength magnesium alloy extruded material which has a composition consisting of 6 to 15% Al, ⁇ 4% Zn and the balance Mg and in which solid-solution Al comprises ⁇ 40% of the Al; (2) a high strength magnesium alloy extruded material composed of the above (1), in which the average grain size of crystals constituting the alloy material in the cross-sectional central part is made to ⁇ 10 ⁇ m; and (3) a high strength magnesium alloy extruded material composed of the above (1) or (2), in which a ratio between the average grain size A of crystals constituting the alloy material in the vicinity of an outer periphery and the average grain size B of crystals constituting the alloy material in the cross-sectional central part satisfies the relation of 1.3
- the magnesium alloy according to Patent Document 1 had a problem that it is still insufficient in heat resistance, i.e. strength at high temperature.
- the magnesium alloy according to Patent Document 2 had a problem that it is necessary to suppress the working degree (rolling reduction ratio) of hot rolling and forging to a low value so as to obtain a defined aspect ratio of crystal grains, so that the strength at room temperature may be sometimes insufficient.
- the magnesium alloys of Patent Documents 1 and 2 may be sometimes insufficient in high-temperature strength or room-temperature strength.
- the environmental temperature necessarily includes a range from room temperature to high temperature. Therefore, it is necessary that tensile characteristics of the magnesium alloy are excellent in both environments at room temperature and high temperature in practical use. Accordingly, a magnesium alloy having sufficient strength at room temperature and high temperature has been required.
- the present invention has been made so as to meet the requirements, and thus an object thereof is to provide a magnesium alloy which has sufficiently high strength at room temperature and high temperature.
- a first aspect of the present invention is directed to a magnesium alloy including: aluminum (Al): 14.0 to 23.0% by mass, calcium (Ca) : 11.0% by mass or less (not including 0% by mass), strontium (Sr): 12.0% by mass or less (not including 0% by mass), and zinc (Zn): 0.2 to 1.0% by mass, and the balance magnesium (Mg) and inevitable impurities, wherein the content of aluminum (A1), the content of calcium (Ca), and the content of strontium (Sr) satisfy a relation shown in the following equation (1): 0.8 ⁇ ⁇ Al > ⁇ 1.35 ⁇ ⁇ Ca > + 1.23 ⁇ ⁇ Sr > + 8.5 ⁇ 1.2 ⁇ ⁇ Al > where ⁇ A1> is the content of aluminum (Al) expressed on % by mass basis, ⁇ Ca> is the content of calcium (Ca) expressed on % by mass basis, and ⁇ Sr> is the content of strontium (Sr) expressed on % by mass basis.
- a second aspect of the present invention is directed to the magnesium alloy according to the first aspect, further including at least one selected from the group consisting of silicon (Si): 0.1 to 1.5% by mass, rare earth (RE): 0.1 to 1.2% by mass, zirconium (Zr): 0.2 to 0.8% by mass, scandium (Sc): 0.2 to 3.0% by mass, yttrium (Y): 0.2 to 3.0 % by mass, tin (Sn): 0.2 to 3.0% by mass, barium (Ba): 0.2 to 3.0% by mass, and antimony (Sb): 0.1 to 1.5% by mass.
- a third aspect of the present invention is the magnesium alloy according to the first or second aspect, in which a ratio of the content of strontium (Sr) to the content of calcium (Ca) is from 1:0.3 to 1:1.5 in terms of a mass ratio.
- a fourth aspect of the present invention is directed to the magnesium alloy according to any one of the first to third aspects, in which precipitates containing Al 2 Ca and Al 4 Sr are formed in the grain boundary with an interval from each other.
- the present inventors have made a study on simultaneous utilization of both solid solution strengthening and precipitation strengthening known as strengthening mechanisms of a magnesium alloy.
- the present inventors have determined solid solubility limit of aluminum in a magnesium alloy matrix and found appropriate amounts of aluminum, calcium and strontium on the basis of the solid solubility limit, and thus completing a magnesium alloy according to the present invention, having sufficient strength at both room temperature and high temperature in which a matrix forms a solid solution with a sufficient amount of aluminum, and also an appropriate amount of intermetallic compounds Al 2 Ca and Al 4 Sr are precipitated.
- Examples of the element capable of being solid-soluted in a magnesium alloy to lower stacking fault energy include In, Tl, Sc, Pb, Al, Y, Sn and Bi. Of these elements, aluminum (Al) is preferable from the viewpoint of safety and economy.
- magnesium alloy is worked into a wrought material by performing plastic working including rolling, extrusion and drawing after casting so as to obtain desired shape, toughness, strength and the like, second phases containing Al 2 Ca and Al 4 Sr precipitating in the grain boundary are fractured (fragmented) and arranged in the deformation direction.
- the precipitates containing Al 2 Ca and Al 4 Sr thus arranged in the deformation direction contribute to an enhancement in high-temperature strength.
- second phase particles containing Al 2 Ca and Al 4 Sr can be reprecipitated and dispersed by performing a homogenization heat treatment at 350 to 450°C, leading to more enhancement in strength. It has also been found that, more preferably, second phases containing Al 2 Ca and Al 4 Sr can be homogeneously dispersed in the grain boundary by performing a homogenization heat treatment at 385°C to 415°C, and thus enabling an increase in strength more certainly.
- the present inventors have found that the amount of aluminum of the magnesium alloy according to the present invention is appropriately from 14.0 to 23.0% by mass.
- the amount of aluminum is 14.0% by mass or more, a sufficient amount of aluminum can form intermetallic compounds Al 2 Ca and Al 4 Sr with calcium and strontium even if about 8.5% by mass of aluminum is solid-soluted in the matrix. If the amount of aluminum is 23.0% by mass or less, it is possible to ensure ductility such as elongation.
- the amount of aluminum is from 15.0% by mass to 20.0% by mass.
- the content of calcium is 11.0% by mass or less (not including 0% by mass).
- the content of calcium is from 1.0 to 8.0% by mass. This is because it is possible to form Al 2 Ca more certainly and to suppress excessiveness.
- the content of strontium is 12.0% by mass or less (not including 0% by mass).
- the content of strontium is from 0.5 to 8.0% by mass. This is because it is possible to form Al 4 Sr more certainly and to suppress excessiveness. More preferably, the content is from 1.0 to 6.0% by mass. This is because it is possible to maximally exert the effect of strontium.
- the magnesium alloy according to the present invention contains 0.2 to 1.0% by mass of zinc (Zn).
- a ratio of (content of calcium):(content of strontium) (content of strontium assumed that the content of calcium is 1) is preferably from 1:0.3 to 1:1.5 in terms of a mass ratio, and more preferably 1:0.5 to 1:1.1 in terms of a mass ratio.
- the amount of aluminum (% by mass) indicated by the symbol y in the equation (2) is required.
- ⁇ Ca> is the content of calcium expressed on % by mass basis and ⁇ Sr> is the content of strontium expressed on % by mass basis.
- aluminum is contained such that the amount of aluminum (y) represented by the equation (2), which is required for entire strontium and calcium to precipitate as Al 2 Ca and Al 4 Sr, respectively, is within a range of the amount which is 0.8 to 1.2 times the content of aluminum.
- the alloy of the present invention contains the above-mentioned aluminum, calcium, strontium and zinc, with the balance being magnesium (Mg) and inevitable impurities.
- Al 2 Ca and Al 4 Sr are often precipitated in the grain boundary, as second phases containing Al 2 Ca and Al 4 Sr, in the form of a network.
- the second phases containing network Al 2 Ca and Al 4 Sr precipitates
- a magnesium alloy article obtained by plastic working (plastic deformation) also has high-temperature strength.
- magnesium alloy according to the present invention (magnesium alloy article (wrought material)) is preferably subjected to a homogenization heat treatment at 350 to 450°C after plastic working.
- a homogenization heat treatment at 350 to 450°C it is preferred to maintain within such temperature range for 24 to 72 hours. This is because this treatment enables redissolution (reprecipitation) of precipitates, leading to an improvement in heat stability.
- the present inventors have also found that a homogenization heat treatment at 385°C to 415°C enables reprecipitation of second phase particles containing Al 2 Ca and Al 4 Sr and homogeneous dispersion of the second phase particles along the grain boundary, leading to further improvement in high-temperature strength.
- a homogenization treatment is performed at 385°C to 415°C after plastic working, second phase particles containing Al 2 Ca and Al 4 Sr (precipitates) are precipitated in the form of particles, instead of a network, with an interval from each other (i.e. discontinuously) along the grain boundary. The thus obtained precipitates in this form remarkably contribute to an improvement in high-temperature strength.
- the magnesium alloy according to the present invention (magnesium alloy article (wrought material)) is preferably subjected to a homogenization heat treatment at 385 to 415°C after plastic working.
- a homogenization heat treatment at 385 to 415°C it is preferred to maintain within such temperature range for 24 to 72 hours. This is because this treatment enables redissolution of precipitates and homogenization of the structure, leading to homogenization and stabilization of an intermetallic compound structure with high heat stability of the grain boundary.
- plastic working includes various hot and cold plastic workings.
- examples of the plastic working include extrusion, rolling, forging, drawing, swaging, and combinations thereof.
- Each alloy sample was melted at 700°C and then cast into a billet using a cylindrical die.
- the casted billet was heated to 400°C at a heating rate of 0.5°C/minute, maintained for 48 hours and then water-cooled. After removing a surface oxide layer by machining, the billet was extruded at an extrusion temperature of 350°C, an extrusion rate of 0.2 mm/second and an extrusion ratio of 16 to obtain a round bar (10 mm in diameter).
- Example 1 In order to examine an influence of a homogenization heat treatment, regarding the above-mentioned sample of Example 1 (extruded round bar), an as-extruded material, a material subjected to a homogenization heat treatment at 400°C for 48 hours, and a material subjected to a homogenization heat treatment at 420°C for 48 hours were produced.
- Figs. 1A to 1C show metallographic structures observed by a confocal laser scanning microscope, in which Fig. 1A shows a metallographic structure of an as-extruded material, Fig. 1B shows a metallographic structure of a material subjected to a homogenization heat treatment at 400°C for 48 hours, and Fig. 1C shows a metallographic structure of a material subjected to a homogenization heat treatment at 420°C for 48 hours.
- precipitates containing Al 2 Ca and Al 4 Sr are fragmented and arranged in the extrusion direction (up/down direction in the drawing).
- precipitates containing Al 2 Ca and Al 4 Sr are dispersed.
- granular precipitates containing comparatively fine Al 2 Ca and Al 4 Sr are homogeneously distributed with an interval from each other along the grain boundary.
- Fig. 2 shows the results of a high-temperature tensile test at 150°C (true stress-strain diagram) of an as-extruded material, a material subjected to a homogenization heat treatment at 400°C for 48 hours, and a material subjected to a homogenization heat treatment at 420°C for 48 hours.
- the tensile test was carried out at a temperature of 150°C and a tension speed of 1 ⁇ 10 -3 /second.
- the material subjected to a homogenization heat treatment at 400°C for 48 hours has high-temperature strength which is remarkably high strength of more than 300 MPa.
- the grain size of each alloy sample is shown in Table 2.
- the grain size was measured by the electron back scattered diffraction patterns (EBSD) method. Crystal grains were defined by regarding deviation of orientation of 15° or more as the grain boundary.
- Comparative Example 3 the grain size could not be measured since precipitates underwent coarsening. Except for Comparative Example 3, the grain size (both peak-top grain size and area average particle size) decreases as addition amounts of aluminum, calcium and strontium increases.
- Fig. 3 shows the measurement results of the tensile strength at room temperature.
- the drawing shows the measurement results of the tensile strength, 0.2% proof stress, and elongation of each alloy sample. In Comparative Examples 2 and 3, 0.2% proof stress could not be measured since the material is brittle.
- Example 1 and Example 2 the tensile strength exhibited excellent value such as 300 MPa or more.
- the 0.2% proof stress is less than 250 MPa, and the samples of Example 1 and Example 2 having the 0.2% proof stress of 250 MPa or more are excellent in room-temperature strength as compared with the samples of Comparative Examples. It is also apparent that the samples of Example 1 and Example 2 exhibit the elongation of 2% or more and have sufficient ductility.
- the sample which is produced by extruding an AZ91 alloy known as a high strength magnesium alloy at an extrusion temperature of 360°C and an extrusion ratio of 22, each being the same level as that of the samples of Examples 1 and 2, exhibits the tensile strength of 295 MPa ( Hanlin Ding et al., Journal of alloys and compounds, 456(2008) 400-406 ). As is apparent from these results, the samples of Examples 1 and 2 have high room-temperature strength.
- Fig. 4 shows the measurement results of high-temperature tensile strength.
- the high-temperature tensile test was carried out at a measuring temperature of 175°C and a strain rate of 1 ⁇ 10 -4 /second.
- Example 1 and Example 2 exhibited high-temperature strength which is higher than that in Comparative Examples, that is, high-temperature strength at 175°C is 210 MPa or more.
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- Mechanical Engineering (AREA)
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Description
- The present invention relates to a magnesium alloy, particularly a magnesium alloy having high strength and high heat resistance, which can be worked into a wrought material such as an extruded or forged material.
- It is known that magnesium is the lightest and has the highest specific strength among practical metals. In order to realize reduction in carbon dioxide emission amount due to weight reduction of vehicles, and extension in travelable distance on one charge of electric cars, as measures to cope with global warming, use of a magnesium alloy is expanded in various applications, for example, application of parts which underwent weight reduction using a magnesium alloy.
- Usually, parts of the magnesium alloy are formed by a casting or die-casting method.
- The reason is as follows. That is, conventional various magnesium alloys can achieve comparatively high room-temperature strength by grain size refinement through plastic working including extrusion, rolling and forging. Meanwhile, since grain boundary precipitates formed into a network undergo fracture, tensile characteristics at high temperature deteriorate, thus leading to limitation of use of a wrought material obtained by plastic working as parts to be used at particularly high temperature.
-
Patent Document 1 discloses that a magnesium alloy containing 0.1 to 15% by weight of calcium and optionally containing aluminum or zinc in the amount which does not exceed two times the amount of calcium is subjected to plastic working including extrusion and rolling, thereby homogeneously dispersing a crushed intermetallic compound in crystal grains, thus leading to an enhancement in mechanical strength. -
Patent Document 2 discloses that refining of crystal grains is suppressed by performing hot rolling or forging at a predetermined processing temperature and rolling reduction ratio using a Mg-Al-Ca-Sr-Mn based alloy, and heat resistance is improved by controlling an aspect ratio of crystal grains (length of a major axis of crystal grains/length of a minor axis of crystal grains) without causing drastic fracture of a network intermetallic compound precipitated in the grain boundary. -
Patent Document 3 relates to the problem to provide an Mg-Al-Zn alloy material which has ≥ 300 MPa tensile strength and uniform mechanical properties and can be easily manufactured by extrusion. As a solution to this problem, the document describes an Mg-Al-Zn alloy material which includes: (1) a high strength magnesium alloy extruded material which has a composition consisting of 6 to 15% Al, ≤ 4% Zn and the balance Mg and in which solid-solution Al comprises ≥ 40% of the Al; (2) a high strength magnesium alloy extruded material composed of the above (1), in which the average grain size of crystals constituting the alloy material in the cross-sectional central part is made to ≤ 10 µm; and (3) a high strength magnesium alloy extruded material composed of the above (1) or (2), in which a ratio between the average grain size A of crystals constituting the alloy material in the vicinity of an outer periphery and the average grain size B of crystals constituting the alloy material in the cross-sectional central part satisfies the relation of 1.3 ≥ A/B ≥ 0.7. -
- Patent Document 1:
JP 2000-109963 A - Patent Document 2:
JP 2007-70688 A - Patent Document 3:
JP 2007-113037 A - However, the magnesium alloy according to
Patent Document 1 had a problem that it is still insufficient in heat resistance, i.e. strength at high temperature. - Meanwhile, the magnesium alloy according to
Patent Document 2 had a problem that it is necessary to suppress the working degree (rolling reduction ratio) of hot rolling and forging to a low value so as to obtain a defined aspect ratio of crystal grains, so that the strength at room temperature may be sometimes insufficient. - Thus, the magnesium alloys of
Patent Documents - Even in the case of a magnesium alloy used at high temperature, the environmental temperature necessarily includes a range from room temperature to high temperature. Therefore, it is necessary that tensile characteristics of the magnesium alloy are excellent in both environments at room temperature and high temperature in practical use. Accordingly, a magnesium alloy having sufficient strength at room temperature and high temperature has been required.
- The present invention has been made so as to meet the requirements, and thus an object thereof is to provide a magnesium alloy which has sufficiently high strength at room temperature and high temperature.
- A first aspect of the present invention is directed to a magnesium alloy including: aluminum (Al): 14.0 to 23.0% by mass, calcium (Ca) : 11.0% by mass or less (not including 0% by mass), strontium (Sr): 12.0% by mass or less (not including 0% by mass), and zinc (Zn): 0.2 to 1.0% by mass, and the balance magnesium (Mg) and inevitable impurities, wherein the content of aluminum (A1), the content of calcium (Ca), and the content of strontium (Sr) satisfy a relation shown in the following equation (1):
- A second aspect of the present invention is directed to the magnesium alloy according to the first aspect, further including at least one selected from the group consisting of silicon (Si): 0.1 to 1.5% by mass, rare earth (RE): 0.1 to 1.2% by mass, zirconium (Zr): 0.2 to 0.8% by mass, scandium (Sc): 0.2 to 3.0% by mass, yttrium (Y): 0.2 to 3.0 % by mass, tin (Sn): 0.2 to 3.0% by mass, barium (Ba): 0.2 to 3.0% by mass, and antimony (Sb): 0.1 to 1.5% by mass.
- A third aspect of the present invention is the magnesium alloy according to the first or second aspect, in which a ratio of the content of strontium (Sr) to the content of calcium (Ca) is from 1:0.3 to 1:1.5 in terms of a mass ratio.
- A fourth aspect of the present invention is directed to the magnesium alloy according to any one of the first to third aspects, in which precipitates containing Al2Ca and Al4Sr are formed in the grain boundary with an interval from each other.
- According to the present invention, it is made possible to provide a magnesium alloy having sufficient room-temperature strength and sufficient high-temperature strength.
-
-
Figs. 1A to 1C show metallographic structures observed by a confocal laser scanning microscope, in whichFig. 1A shows a metallographic structure of an as-extruded material,Fig. 1B shows a metallographic structure of a material subjected to a homogenization heat treatment at 400°C for 48 hours, andFig. 1C shows a metallographic structure of a material subjected to a homogenization heat treatment at 420°C for 48 hours. -
Fig. 2 shows the results of a high-temperature tensile test at 150°C (true stress-strain diagram) of an as-extruded material, a material subjected to a homogenization heat treatment at 400°C for 48 hours, and a material subjected to a homogenization heat treatment at 420°C for 48 hours. -
Fig. 3 shows the measurement results of a tensile strength at room temperature. -
Fig. 4 shows the measurement results of a tensile strength at high temperature. - The present inventors have made a study on simultaneous utilization of both solid solution strengthening and precipitation strengthening known as strengthening mechanisms of a magnesium alloy.
- That is, they have made a study on effective actuation of both solid solution strengthening mechanism and precipitation strengthening mechanism by appropriate control of the contents of aluminum, strontium and calcium.
- Subsequently, the present inventors have determined solid solubility limit of aluminum in a magnesium alloy matrix and found appropriate amounts of aluminum, calcium and strontium on the basis of the solid solubility limit, and thus completing a magnesium alloy according to the present invention, having sufficient strength at both room temperature and high temperature in which a matrix forms a solid solution with a sufficient amount of aluminum, and also an appropriate amount of intermetallic compounds Al2Ca and Al4Sr are precipitated.
- Detailed description will be made below.
- In the deformation at high temperature of the magnesium alloy, low stacking fault energy suppresses the movement of dislocations, resulting in the difficulty in deformation. Thus, if stacking fault energy can be lowered, heat resistance (high-temperature strength and creep) can be improved.
- Examples of the element capable of being solid-soluted in a magnesium alloy to lower stacking fault energy include In, Tl, Sc, Pb, Al, Y, Sn and Bi. Of these elements, aluminum (Al) is preferable from the viewpoint of safety and economy.
- As a result of the present inventors' study, it has been found the addition of calcium (Ca) and strontium (Sr), together with aluminum, enables refining of the grain size, leading to an enhancement in room-temperature strength, and also intermetallic compounds Al2Ca and Al4Sr to be precipitated (crystallized) exist in the grain boundary, together with other second phases (precipitates), thereby improving room temperature and high temperature characteristics.
- If the magnesium alloy is worked into a wrought material by performing plastic working including rolling, extrusion and drawing after casting so as to obtain desired shape, toughness, strength and the like, second phases containing Al2Ca and Al4Sr precipitating in the grain boundary are fractured (fragmented) and arranged in the deformation direction.
- The precipitates containing Al2Ca and Al4Sr thus arranged in the deformation direction contribute to an enhancement in high-temperature strength.
- However, the present inventors have intensively studied and found that second phase particles containing Al2Ca and Al4Sr can be reprecipitated and dispersed by performing a homogenization heat treatment at 350 to 450°C, leading to more enhancement in strength. It has also been found that, more preferably, second phases containing Al2Ca and Al4Sr can be homogeneously dispersed in the grain boundary by performing a homogenization heat treatment at 385°C to 415°C, and thus enabling an increase in strength more certainly.
- As a result of the continued study, the present inventors have found that maximum solubility (solid solubility limit) of aluminum in matrix of the sample subjected to a homogenization heat treatment at 400°C for 48 hours after plastic working such as extrusion is 8.3% by mass (7.5 atomic %). The measurement was performed by point analysis using an electron probe microanalyzer (EPMA).
- Using this solid solubility limit, the present inventors have found that the amount of aluminum of the magnesium alloy according to the present invention is appropriately from 14.0 to 23.0% by mass.
- The reason is that, if the amount of aluminum is 14.0% by mass or more, a sufficient amount of aluminum can form intermetallic compounds Al2Ca and Al4Sr with calcium and strontium even if about 8.5% by mass of aluminum is solid-soluted in the matrix. If the amount of aluminum is 23.0% by mass or less, it is possible to ensure ductility such as elongation.
- More preferably, the amount of aluminum is from 15.0% by mass to 20.0% by mass.
- This is because it is possible to form intermetallic compounds Al2Ca and Al4Sr more certainly and to ensure ductility if the amount of aluminum is within the above range.
- The content of calcium is 11.0% by mass or less (not including 0% by mass).
- The maximum content (11.0% by mass) of calcium is almost equal to the amount of calcium required for almost all aluminum, which was not solid-soluted, to form Al2Ca ((upper limit of aluminum - maximum solubility)/atomic weight of Al × atomic ratio of Ca to Al of Al2Ca × atomic weight of Ca = 10.9). Thus, it is made possible to certainly precipitate aluminum, which is not solid-soluted, as a desired intermetallic compound.
- In order to ensure inclusion of calcium, 0% by mass is excluded.
- More preferably, the content of calcium is from 1.0 to 8.0% by mass. This is because it is possible to form Al2Ca more certainly and to suppress excessiveness.
- The content of strontium is 12.0% by mass or less (not including 0% by mass).
- The maximum content (12.0% by mass) of strontium is almost equal to the amount of calcium required for almost all aluminum, which was not solid-soluted, to form Al4Sr ((upper limit of aluminum - maximum solubility)/atomic weight of Al ×atomic ratio of Sr to Al of Al4Sr × atomic weight of Sr = 11.9). Thus, it is made possible to certainly precipitate aluminum, which is not solid-soluted, as a desired intermetallic compound.
- In order to ensure inclusion of strontium, 0% by mass is excluded.
- Preferably, the content of strontium is from 0.5 to 8.0% by mass. This is because it is possible to form Al4Sr more certainly and to suppress excessiveness. More preferably, the content is from 1.0 to 6.0% by mass. This is because it is possible to maximally exert the effect of strontium.
- The magnesium alloy according to the present invention contains 0.2 to 1.0% by mass of zinc (Zn).
- This is because zinc has the effect of enhancing the strength and the effect of improving castability.
- In order to form both intermetallic compounds Al2Ca and Al4Sr in a more suitable ratio (ratio of formation amount of Al2Ca and Al4Sr), a ratio of (content of calcium):(content of strontium) (content of strontium assumed that the content of calcium is 1) is preferably from 1:0.3 to 1:1.5 in terms of a mass ratio, and more preferably 1:0.5 to 1:1.1 in terms of a mass ratio.
-
- In this equation, <Ca> is the content of calcium expressed on % by mass basis and <Sr> is the content of strontium expressed on % by mass basis.
- Physical meaning of a numerical value in the equation is shown in parentheses behind the numerical value.
- In the magnesium alloy according to the present invention, it is necessary to satisfy the following equation (1).
- That is, aluminum is contained such that the amount of aluminum (y) represented by the equation (2), which is required for entire strontium and calcium to precipitate as Al2Ca and Al4Sr, respectively, is within a range of the amount which is 0.8 to 1.2 times the content of aluminum.
- This is because, when the content of aluminum is within a range represented by the equation (1), Al2Ca and Al4Sr, which are almost equal to the stoichiometric composition, are precipitated and also aluminum is sufficiently solid-soluted in the matrix in just proportion of all elements of aluminum, calcium and strontium.
- The alloy of the present invention contains the above-mentioned aluminum, calcium, strontium and zinc, with the balance being magnesium (Mg) and inevitable impurities.
- Al2Ca and Al4Sr are often precipitated in the grain boundary, as second phases containing Al2Ca and Al4Sr, in the form of a network. As mentioned above, when subjected to plastic working, the second phases containing network Al2Ca and Al4Sr (precipitates) tend to be fractured (fragmented) and arranged in the deformation direction.
- Since the thus fragmented precipitates containing Al2Ca and Al4Sr contribute to an improvement in high-temperature strength, a magnesium alloy article (magnesium alloy wrought material) obtained by plastic working (plastic deformation) also has high-temperature strength.
- However, second phase particles containing Al2Ca and Al4Sr can be reprecipitated and dispersed by performing a homogenization heat treatment at 350 to 450°C after plastic working, thereby finding that high-temperature strength can be more enhanced. Therefore, the magnesium alloy according to the present invention (magnesium alloy article (wrought material)) is preferably subjected to a homogenization heat treatment at 350 to 450°C after plastic working. In the homogenization heat treatment at 350 to 450°C, it is preferred to maintain within such temperature range for 24 to 72 hours. This is because this treatment enables redissolution (reprecipitation) of precipitates, leading to an improvement in heat stability.
- The present inventors have also found that a homogenization heat treatment at 385°C to 415°C enables reprecipitation of second phase particles containing Al2Ca and Al4Sr and homogeneous dispersion of the second phase particles along the grain boundary, leading to further improvement in high-temperature strength. In case a homogenization treatment is performed at 385°C to 415°C after plastic working, second phase particles containing Al2Ca and Al4Sr (precipitates) are precipitated in the form of particles, instead of a network, with an interval from each other (i.e. discontinuously) along the grain boundary. The thus obtained precipitates in this form remarkably contribute to an improvement in high-temperature strength. Therefore, the magnesium alloy according to the present invention (magnesium alloy article (wrought material)) is preferably subjected to a homogenization heat treatment at 385 to 415°C after plastic working. In the homogenization heat treatment at 385 to 415°C, it is preferred to maintain within such temperature range for 24 to 72 hours. This is because this treatment enables redissolution of precipitates and homogenization of the structure, leading to homogenization and stabilization of an intermetallic compound structure with high heat stability of the grain boundary.
- As used herein, plastic working includes various hot and cold plastic workings. Examples of the plastic working include extrusion, rolling, forging, drawing, swaging, and combinations thereof.
- Alloy samples, each containing components shown in Table 1, were prepared.
- The value y in the equation (2) of samples of Examples (Example 1 and Example 2) shown in Table 1 is 15.5 in Example 1 and is 20.9 in Example, and therefore alloy samples satisfy the equation (1). In both Example 1 and Example 2, a ratio of (content of calcium):(content of strontium) is 1:1 in terms of a mass ratio.
Table 1 Comparative Example 1 Example 1 Example 2 Comparative Example 2 Comparative Example 3 Mass % Atomic % Mass % Atomic % Mass % Atomic % Mass % Atomic % Mass % Atomic % Mg 88.1 90.0 79.1 80.8 69.9 71.4 60.9 62.2 51.9 53.0 Al 10.0 9.2 15.0 13.8 20.0 18.4 25.0 23.0 30.0 27.6 Ca 0.7 0.4 2.7 1.7 4.8 3.0 6.8 4.2 8.8 5.5 Sr 0.7 0.2 2.7 0.8 4.8 1.4 6.8 1.9 8.8 2.5 Zn 0.5 0.2 0.5 0.2 0.5 0.2 0.5 0.2 0.5 0.2 - Each alloy sample was melted at 700°C and then cast into a billet using a cylindrical die. The casted billet was heated to 400°C at a heating rate of 0.5°C/minute, maintained for 48 hours and then water-cooled. After removing a surface oxide layer by machining, the billet was extruded at an extrusion temperature of 350°C, an extrusion rate of 0.2 mm/second and an extrusion ratio of 16 to obtain a round bar (10 mm in diameter).
- In order to examine an influence of a homogenization heat treatment, regarding the above-mentioned sample of Example 1 (extruded round bar), an as-extruded material, a material subjected to a homogenization heat treatment at 400°C for 48 hours, and a material subjected to a homogenization heat treatment at 420°C for 48 hours were produced.
-
Figs. 1A to 1C show metallographic structures observed by a confocal laser scanning microscope, in whichFig. 1A shows a metallographic structure of an as-extruded material,Fig. 1B shows a metallographic structure of a material subjected to a homogenization heat treatment at 400°C for 48 hours, andFig. 1C shows a metallographic structure of a material subjected to a homogenization heat treatment at 420°C for 48 hours. - In the as-extruded material, precipitates containing Al2Ca and Al4Sr (second phases) are fragmented and arranged in the extrusion direction (up/down direction in the drawing). In contrast, in the material subjected to a homogenization heat treatment at 400°C for 48 hours and the material subjected to a homogenization heat treatment at 420°C for 48 hours, precipitates containing Al2Ca and Al4Sr (second phases) are dispersed. Particularly in the material subjected to a homogenization heat treatment at 400°C for 48 hours, granular precipitates containing comparatively fine Al2Ca and Al4Sr are homogeneously distributed with an interval from each other along the grain boundary.
-
Fig. 2 shows the results of a high-temperature tensile test at 150°C (true stress-strain diagram) of an as-extruded material, a material subjected to a homogenization heat treatment at 400°C for 48 hours, and a material subjected to a homogenization heat treatment at 420°C for 48 hours. The tensile test was carried out at a temperature of 150°C and a tension speed of 1 × 10-3/second. - All samples exhibit excellent high-temperature strength (heat resistance), that is, tensile strength at 150°C of 250 MPa. Of these, the material subjected to a homogenization heat treatment at 400°C for 48 hours and the material subjected to a homogenization heat treatment at 420°C for 48 hours exhibit high-temperature strength which is higher than that of the as-extruded material. Particularly, the material subjected to a homogenization heat treatment at 400°C for 48 hours has high-temperature strength which is remarkably high strength of more than 300 MPa.
- Considering the above results, subsequent evaluation was carried out after homogenizing the extruded round bars of Examples 1 and 2 as well as Comparative Examples 1 to 3 at 400°C for 48 hours and processing them into tensile test specimens.
- The grain size of each alloy sample is shown in Table 2.
- The grain size was measured by the electron back scattered diffraction patterns (EBSD) method. Crystal grains were defined by regarding deviation of orientation of 15° or more as the grain boundary.
- The average grain size was determined by simply dividing the total area by the number of crystal grains.
Table 2 Alloy Grain size (µm) Comparative Example 1 20.1 Example 1 9.2 Example 2 4.9 Comparative Example 2 4.2 Comparative Example 3 - - In Comparative Example 3, the grain size could not be measured since precipitates underwent coarsening. Except for Comparative Example 3, the grain size (both peak-top grain size and area average particle size) decreases as addition amounts of aluminum, calcium and strontium increases.
-
Fig. 3 shows the measurement results of the tensile strength at room temperature. The drawing shows the measurement results of the tensile strength, 0.2% proof stress, and elongation of each alloy sample. In Comparative Examples 2 and 3, 0.2% proof stress could not be measured since the material is brittle. - In Comparative Example 1, Example 1 and Example 2, the tensile strength exhibited excellent value such as 300 MPa or more. However, it is apparent that, in Comparative Example 1, the 0.2% proof stress is less than 250 MPa, and the samples of Example 1 and Example 2 having the 0.2% proof stress of 250 MPa or more are excellent in room-temperature strength as compared with the samples of Comparative Examples. It is also apparent that the samples of Example 1 and Example 2 exhibit the elongation of 2% or more and have sufficient ductility.
- It is also known that the sample, which is produced by extruding an AZ91 alloy known as a high strength magnesium alloy at an extrusion temperature of 360°C and an extrusion ratio of 22, each being the same level as that of the samples of Examples 1 and 2, exhibits the tensile strength of 295 MPa (Hanlin Ding et al., Journal of alloys and compounds, 456(2008) 400-406). As is apparent from these results, the samples of Examples 1 and 2 have high room-temperature strength.
-
Fig. 4 shows the measurement results of high-temperature tensile strength. The high-temperature tensile test was carried out at a measuring temperature of 175°C and a strain rate of 1 × 10-4/second. - Since the sample of Comparative Example 3 was fractured soon after applying tensile stress, high-temperature strength could not be measured.
- The samples of Example 1 and Example 2 exhibited high-temperature strength which is higher than that in Comparative Examples, that is, high-temperature strength at 175°C is 210 MPa or more.
- As is apparent from the above results, the samples of Examples exhibit high strength at both room temperature and high temperature.
Claims (4)
- A magnesium alloy comprising:aluminum (Al): 14.0 to 23.0% by mass,calcium (Ca): 11.0% by mass or less (not including 0% by mass),strontium (Sr): 12.0% by mass or less (not including 0% by mass),zinc (Zn): 0.2 to 1.0% by mass, and optionally Si, RE, Zr, Sc, Y, Sn, Ba, Sb,the balance magnesium (Mg) and inevitable impurities, wherein the content of aluminum (Al), the content of calcium (Ca), and the content of strontium (Sr) satisfy a relation shown in the following equation (1):
- The magnesium alloy according to claim 1, further comprising at least one selected from the group consisting of:silicon (Si): 0.1 to 1.5% by mass,rare earth (RE): 0.1 to 1.2% by mass,zirconium (Zr): 0.2 to 0.8% by mass,scandium (Sc): 0.2 to 3.0% by mass,yttrium (Y): 0.2 to 3.0 % by mass,tin (Sn): 0.2 to 3.0% by mass,barium (Ba): 0.2 to 3.0% by mass, andantimony (Sb): 0.1 to 1.5% by mass.
- The magnesium alloy a ccording to claim 1 or 2, wherein a ratio of the content of strontium (Sr) to the content of calcium (Ca) is from 1:0.3 to 1:1.5 in terms of a mass ratio.
- The magnesium alloy according to any one of claims 1 to 3, wherein precipitates containing Al2Ca and Al4Sr are formed in the grain boundary with an interval from each other.
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JP2011072505A JP5729081B2 (en) | 2011-03-29 | 2011-03-29 | Magnesium alloy |
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KR101933589B1 (en) * | 2015-12-28 | 2018-12-31 | 한국기계연구원 | Magnesium Alloys having improved mechanical properties and corrosion resistance and method for manufacturing the same |
CN108474067A (en) * | 2016-07-15 | 2018-08-31 | 住友电气工业株式会社 | Magnesium alloy |
CN108220724A (en) * | 2017-12-22 | 2018-06-29 | 中山市榄商置业发展有限公司 | A kind of magnesium alloy new material and its preparation process |
CN109182860A (en) * | 2018-11-08 | 2019-01-11 | 中信戴卡股份有限公司 | A kind of magnesium alloy with high strength and ductility and preparation method |
AT522003B1 (en) * | 2018-12-18 | 2021-10-15 | Lkr Leichtmetallkompetenzzentrum Ranshofen Gmbh | Magnesium base alloy and process for making the same |
CN109913720B (en) * | 2019-03-27 | 2020-11-24 | 东北大学 | High-calcium high-aluminum-content high-elasticity-modulus magnesium-based composite material and preparation method thereof |
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