WO2011071024A1 - マグネシウム合金材 - Google Patents
マグネシウム合金材 Download PDFInfo
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- WO2011071024A1 WO2011071024A1 PCT/JP2010/071849 JP2010071849W WO2011071024A1 WO 2011071024 A1 WO2011071024 A1 WO 2011071024A1 JP 2010071849 W JP2010071849 W JP 2010071849W WO 2011071024 A1 WO2011071024 A1 WO 2011071024A1
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- magnesium alloy
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 128
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- 238000009864 tensile test Methods 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 46
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
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- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910003023 Mg-Al Inorganic materials 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
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- 238000010119 thixomolding Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
Definitions
- the present invention relates to a magnesium alloy material suitable as a constituent material for various parts such as automobile parts and casings of portable electric devices.
- a magnesium alloy material excellent in impact resistance relates to a magnesium alloy material excellent in impact resistance.
- Magnesium alloys that are lightweight and have excellent specific strength and specific rigidity have been studied as constituent materials for various parts such as casings for portable electrical devices such as mobile phones and notebook personal computers, and automobile parts such as wheel covers and paddle shifters. ing.
- Parts made of magnesium alloys are mainly cast materials (ASTM standard AZ91 alloy) by die casting or thixomolding.
- ASTM standard AZ31 alloy a plate made of a magnesium alloy for spreading represented by ASTM standard AZ31 alloy is being used.
- Patent Documents 1 and 2 disclose that a rolled plate made of an AZ91 alloy or an alloy containing Al at the same level as the AZ91 alloy is manufactured under specific conditions and subjected to press working.
- Magnesium is said to have excellent vibration energy absorption characteristics.
- an alloy content that reduces Al content or does not contain Zn specifically, an ASTM standard AM60 alloy is used.
- the above AM60 alloy is excellent in impact resistance, further improvement is desired.
- the internal defect such as the nest is likely to exist, and the Al component is locally high concentration, the crystal grains are randomly oriented, etc. Tissue tends to be uneven.
- a cast material such as a die-cast material made of an AZ91 alloy since the content of Al is large, Al does not completely dissolve and tends to precipitate as an intermetallic compound at the crystal grain boundary.
- Casting materials such as die-cast materials made of AZ91 alloy have high impact resistance due to the above-mentioned defects and grain boundary precipitates becoming the starting point of fracture, and the above-mentioned composition and non-uniform structure are mechanical weak points. Inferior.
- an object of the present invention is to provide a magnesium alloy material having excellent impact resistance.
- the present inventors aimed at a magnesium alloy containing more than 7.5% by mass of Al, and produced plates by various manufacturing methods using this magnesium alloy. . And the impact resistance of the obtained board was investigated. As a result, it has been found that a magnesium alloy sheet produced under specific production conditions is very excellent in impact resistance.
- a precipitate such as an intermetallic compound containing at least one of Mg and Al such as Mg 17 Al 12 and Al 6 (MnFe) in the magnesium alloy was investigated.
- the precipitate particles were relatively small and uniformly dispersed, and coarse particles of 5 ⁇ m or more were not substantially present. Therefore, a method for controlling the particle size and the amount of the precipitates, that is, preventing the generation of coarse precipitates as described above and producing a certain amount of fine precipitates was studied.
- the manufacturing conditions are controlled so that the total time for keeping the magnesium alloy material in a specific temperature range is within a specific range. It was found that it is preferable to do this.
- the present invention is based on the above findings.
- the present invention relates to a magnesium alloy material made of a magnesium alloy containing Al in excess of 7.5% by mass, and has a Charpy impact value of 30 J / cm 2 or more.
- the magnesium alloy material of the present invention has a very large impact absorption energy, and has a Charpy impact value equal to or higher than that of AM60 alloy as shown in a test example described later, and is excellent in impact resistance. Therefore, when the magnesium alloy material of the present invention is used as a constituent material of a component that is desired to sufficiently absorb energy at the time of impact, such as an automobile component, even if stress is applied at a high speed, it is easily cracked. It does not occur and is expected to absorb shocks sufficiently. Therefore, it is expected that the magnesium alloy material of the present invention can be suitably used as a constituent material of the impact absorbing member.
- the larger the Charpy impact value the greater the impact absorption energy, so 40 J / cm 2 or more is more preferable, and there is no upper limit.
- the magnesium alloy material of the present invention contains more Al than AM60 alloy, so that it has excellent corrosion resistance compared to AM60 alloy. Especially this invention magnesium alloy material is excellent in corrosion resistance also from having a specific structure
- the elongation in a high-speed tensile test at a tensile speed of 10 m / sec is 10% or more.
- the magnesium alloy material of the present invention has a tensile rate of 10 m / sec, although the elongation in a general tensile test (tensile speed: about several mm / sec) is slightly inferior to that of the AM60 alloy.
- the surprising result was that the elongation in the tensile test at such a high speed was higher than that of the AM60 alloy.
- the magnesium alloy material of the present invention has such a high elongation in the high-speed tensile test, it is expected that the magnesium alloy material can be sufficiently deformed to absorb the shock when subjected to an impact (when an object contacts at a high speed). It is considered that the greater the elongation, the better the impact resistance, and it is preferably 12% or more, more preferably 14% or more, and no upper limit is set.
- the tensile strength in a high-speed tensile test at a tensile speed of 10 m / sec is 300 MPa or more.
- the magnesium alloy material of the present invention has high elongation and high toughness in the high-speed tensile test as described above, and also has high tensile strength and high strength in the high-speed tensile test.
- the tensile strength is preferably as high as possible, 320 MPa or more, more preferably over 330 MPa, and no upper limit.
- the elongation EL hg in a high-speed tensile test at a tensile speed of 10 m / sec is 1.3 times or more of the elongation EL low in a low-speed tensile test at a tensile speed of 2 mm / sec.
- the elongation in the said high-speed tensile test is high, and the difference with the elongation in the said low-speed tensile test is large.
- the AM60 alloy has a high elongation in the high-speed tensile test as shown in the test examples described later, but the elongation is almost the same as the elongation in the low-speed tensile test.
- the absolute value of the elongation in the high-speed tensile test is high and the difference from the elongation in the low-speed tensile test is large. It can be said that it has the ability possible. Therefore, according to the said form, it is excellent in impact resistance.
- a form satisfying EL hg ⁇ 1.5 ⁇ EL low can be obtained.
- particles of precipitates are present dispersed in the magnesium alloy, and the average particle size of the particles of these precipitates is 0.05 ⁇ m or more and 1 ⁇ m or less, and in the cross section of the magnesium alloy material A form in which the ratio of the total area of the precipitate particles is 1% or more and 20% or less is mentioned.
- the magnesium alloy material of the present invention is difficult to dent even when subjected to an impact due to the improvement in rigidity of the plate itself by the dispersion strengthening of the precipitates, and is excellent in impact resistance characteristics.
- the magnesium alloy material of the present invention is excellent in impact resistance because it was possible to maintain the strength by suppressing the decrease in strength. Therefore, the magnesium alloy material of the present invention having the above specific structure is excellent in impact resistance.
- the magnesium alloy material of the present invention since there are few coarse precipitates, it is excellent also in plastic workability, and press work can be performed easily.
- the particles of the precipitate may include particles composed of an intermetallic compound containing at least one of Al and Mg.
- the intermetallic compounds tend to have better corrosion resistance than magnesium alloys. Therefore, according to the said form, in addition to the impact resistance improvement by the dispersion
- the magnesium alloy material of the present invention is excellent in impact resistance.
- FIG. 1 is a graph showing the Charpy impact value of a magnesium alloy material.
- FIG. 2 is a graph showing elongation in a high-speed tensile test and a low-speed tensile test of a magnesium alloy material.
- FIG. 3 is a graph showing the tensile strength of a magnesium alloy material in a high-speed tensile test and a low-speed tensile test.
- FIG. 4 is a graph showing 0.2% proof stress in a high-speed tensile test and a low-speed tensile test of a magnesium alloy material.
- FIG. 5 is a plan view of a test piece used in the high-speed tensile test. 6 is a micrograph (magnification 5000) of the magnesium alloy material, FIG.
- FIG. 6 (I) shows Sample No. 1
- FIG. 6 (II) shows Sample No. 110.
- FIG. 7 is a micrograph of a cross section of a magnesium alloy member having an anticorrosion layer
- FIG. 7 (I) is Sample No. 1 (250,000 times)
- FIG. 7 (II) is Sample No. 110 (100,000 times). ).
- the magnesium alloy constituting the magnesium alloy material of the present invention includes those having various compositions containing an additive element in Mg (remainder: Mg and impurities, Mg: 50% by mass or more).
- Mg residual material
- impurities Mg: 50% by mass or more
- an Mg-Al alloy containing at least 7.5% by mass of Al as an additive element is used.
- the mechanical properties such as strength and plastic deformation resistance of the magnesium alloy itself can be improved, and the corrosion resistance is also excellent.
- the content of Al is preferably 12% by mass or less.
- Additive elements other than Al were selected from Zn, Mn, Si, Ca, Sr, Y, Cu, Ag, Be, Sn, Li, Zr, Ce, Ni, Au, and rare earth elements (excluding Y and Ce)
- Mg-Al alloys include, for example, AZ alloys (Mg-Al-Zn alloys, Zn: 0.2 mass% to 1.5 mass%) and AM alloys (Mg-Al-Mn alloys) according to ASTM standards.
- Mn 0.15 mass% to 0.5 mass%)
- Mg-Al-RE rare earth element
- AX alloy Mg-Al-Ca alloy, Ca: 0.2 mass% to 6.0 mass%)
- AJ alloy Mg—Al—Sr alloy, Sr: 0.2 mass% to 7.0 mass%)
- the form containing 8.3 mass% to 9.5 mass% of Al is excellent in strength and corrosion resistance.
- an Mg-Al alloy containing 8.3% to 9.5% by mass of Al and 0.5% to 1.5% by mass of Zn typically an AZ91 alloy.
- the magnesium alloy has a structure in which fine precipitates having an average particle size of 0.05 ⁇ m to 1 ⁇ m are dispersed. When the cross section of the magnesium alloy material is taken and the magnesium alloy material is 100% by area, the precipitate Is present from 1 area% to 20 area%.
- the precipitate contains an additive element in the magnesium alloy, typically an intermetallic compound containing Mg or Al, more specifically composed of Mg 17 Al 12 (not limited to Mg 17 Al 12 ) Is mentioned. With an average particle size of 0.05 ⁇ m or more and a precipitate content of 1 area% or more, there are sufficient precipitates in the magnesium alloy, and excellent impact resistance is achieved by dispersion strengthening of these precipitates. Can have sex.
- the average particle size of the precipitate is 1 ⁇ m or less and the content of the precipitate is 20 area% or less, there is no precipitate in the magnesium alloy, or there is no coarse precipitate. Suppresses a decrease in the amount of solid solution, and is excellent in strength.
- a more preferable average particle diameter is 0.1 ⁇ m or more and 0.5 ⁇ m or less, and a more preferable precipitate content is 3 area% or more and 15 area% or less, further 12 area% or less, and particularly 5 area% or more and 10 area% or less.
- the magnesium alloy material of the present invention typically includes a rectangular plate material (magnesium alloy plate), and may take various shapes such as a circular shape as well as a rectangular shape.
- This plate-like material can take the form of a coil material obtained by winding a continuous long material, or a short material having a predetermined length and shape.
- this plate-shaped material can be made into the form which has the hole etc. which the boss
- this plate-like material can take various forms depending on the manufacturing process.
- the magnesium alloy material of the present invention includes a molded body obtained by subjecting the plate-like material to plastic working such as press working such as bending or drawing.
- the form, size (area) and thickness of the magnesium alloy material may be selected. In particular, when the thickness is 2.0 mm or less, further 1.5 mm or less, particularly 1 mm or less, it can be suitably used for thin and lightweight parts (typically, housings and automobile parts).
- the molded body is, for example, a cross-sectional box having a top plate portion (bottom surface portion) and a side wall portion erected from the periphery of the top plate portion, a frame-like frame body, and the top plate portion being a disc.
- the shape and size are not particularly limited, such as a covered cylindrical body having a cylindrical side wall portion.
- the top plate or the like has a boss or the like formed or joined integrally, has a hole penetrating the front and back, a groove recessed in the thickness direction, has a stepped shape, plastic processing or cutting processing It may have a portion where the thickness is locally different.
- this invention magnesium alloy material can be made into the form which provides the plastic processing part to which plastic processing called press processing was given only in part.
- the portion where the deformation due to plastic deformation is small is the plate that is the material for plastic working.
- the structure and mechanical properties of the shaped material (magnesium alloy plate) are generally maintained. Therefore, in the form having a molded body and a plastic working part, when measuring mechanical properties such as Charpy impact value and elongation, test specimens are collected from locations where there is little deformation due to the plastic deformation.
- the magnesium alloy material of the present invention is characterized in that the Charpy impact value, the elongation in the high-speed tensile test, and the tensile strength are equal to or greater than those of the AM60 alloy as described above.
- the magnesium alloy material of the present invention bends without breaking (breaking) when the Charpy impact test is performed, that is, when stress is applied at a high speed, as shown in a test example described later.
- the magnesium alloy material of the present invention is sufficiently plastically deformed when subjected to an impact, and can absorb the energy at the time of the impact by deformation. For example, when used as a constituent material of an automobile part such as a chassis or a bumper. It is expected to contribute to the protection of passengers in the car.
- the magnesium alloy material of the present invention can be a magnesium alloy member having on its surface an anticorrosive layer formed by surface treatment such as chemical conversion treatment or anodizing treatment.
- the magnesium alloy member is further excellent in corrosion resistance by including a corrosion prevention layer in addition to the magnesium alloy material of the present invention which is also excellent in corrosion resistance.
- the anticorrosion layer may have a specific structure (double layer structure). And the magnesium alloy member which has this anticorrosion layer of the specific structure was very excellent in corrosion resistance.
- a specific structure of the anticorrosion layer is a two-layer structure including a lower layer formed on the magnesium alloy material side and a surface layer formed on the lower layer.
- the surface layer is denser than the lower layer, and this lower layer is a porous layer.
- the anticorrosion layer is very thin, and the total thickness of the anticorrosion layer having a two-layer structure is 50 nm to 300 nm (the lower layer is about 60% to 75% of the thickness).
- the magnesium alloy material of the present invention having the above specific structure is a plate-like material, it can be produced, for example, by a method for producing a magnesium alloy plate comprising the following steps.
- Preparation step A step of preparing a cast plate made of a magnesium alloy containing Al in excess of 7.5% by mass and manufactured by a continuous casting method.
- Solution treatment step A step of producing a solid solution plate by subjecting the cast plate to a solution treatment at a temperature of 350 ° C. or higher.
- Rolling step A step of producing a rolled plate by subjecting the solid solution plate to warm rolling.
- the total time for maintaining the material plate (typically a rolled sheet) to be processed in a temperature range of 150 ° C. or more and 300 ° C. or less is 0.5 hours or more and 12 hours or less.
- the thermal history of the material plate is controlled so as not to be heated to a temperature exceeding 300 ° C.
- the manufacturing method can include a correction process for correcting the rolled plate.
- straightening is performed in a state where the rolled sheet is heated to 100 ° C. or higher and 300 ° C. or lower, that is, warm correction is performed.
- a time for holding the rolled sheet in the temperature range of 150 ° C. or more and 300 ° C. or less in the straightening process is included in the total time.
- the form in which the magnesium alloy material of the present invention is a molded body and the form having a plastic working part are, for example, a rolled plate obtained by the above-described method for producing a magnesium alloy plate as a material, and a straightening obtained by the straightening process.
- a plate can be prepared, and can be manufactured by a manufacturing method including a plastic processing step in which plastic processing is performed on the material.
- the magnesium alloy member comprising the magnesium alloy material of the present invention and the anticorrosion layer is produced, for example, by a manufacturing method comprising a surface treatment step of subjecting the plastic-processed material to a chemical conversion treatment or an anodizing treatment. Can be manufactured.
- the anticorrosion layer formed by the surface treatment can be prevented from being damaged during the plastic working.
- the anticorrosion treatment can be applied to the material before the plastic working.
- a step of preparing a rolled plate or a correction plate as described above on the material a step of applying an anticorrosion treatment to the material, and a step of applying the plastic working after the anticorrosion treatment
- a method of providing in this manufacturing method since the anticorrosion treatment target is a flat shape such as a plate-like material, the anticorrosion treatment can be easily performed.
- the magnesium alloy material of the present invention Al is sufficiently dissolved in the magnesium alloy by performing the solution treatment as described above. Then, in the manufacturing process after the solution treatment, by keeping the material composed of the magnesium alloy in a temperature range (150 ° C. to 300 ° C.) in which the precipitate is likely to be precipitated within a specific range, While precipitating, the amount can be within a specific range. In addition, by controlling the time for holding in the specific temperature range, excessive growth of the precipitate can be suppressed, and a structure in which fine precipitates are dispersed can be obtained.
- a workpiece solution-treated material.
- the plastic workability is improved and rolling is easy.
- the Al content is as high as more than 7.5% by mass, so that precipitates such as the above-mentioned intermetallic compounds are likely to be deposited, or the deposited precipitates grow and become coarse particles It becomes easy to become.
- precipitates are generated excessively or grow coarsely, the amount of solid solution of Al in the magnesium alloy decreases. And the fall of the strength and corrosion resistance of magnesium alloy itself is caused by the fall of the solid solution amount of Al. Further, due to the decrease in the amount of Al dissolved, it is difficult to further improve the corrosion resistance even if the anticorrosion layer is formed.
- Patent Document 1 proposes that heat treatment (final annealing) after rolling is performed at 300 ° C. to 340 ° C. for the AZ91 alloy. Even when the heat treatment is performed at a heating temperature of more than 300 ° C., the precipitate grows and tends to become coarse particles. From these things, it proposes controlling the heat history of a raw material board with respect to the process after solution forming as mentioned above.
- the cast plate it is preferable to use a cast plate produced by a continuous casting method such as a twin-roll method, in particular, a casting method described in WO / 2006/003899. Since the continuous casting method can be rapidly solidified, it can reduce oxides and segregation, and can suppress the formation of coarse crystal precipitates exceeding 10 ⁇ m that can be the starting point of cracking. Therefore, a cast plate having excellent rolling properties can be obtained.
- the size of the cast plate is not particularly limited, but segregation is likely to occur if it is too thick.
- the cast plate is subjected to a solution treatment so that the composition is homogenized and a solid solution plate in which an element such as Al is dissolved is manufactured.
- the solution treatment is preferably performed at a holding temperature of 350 ° C. or higher, particularly a holding temperature: 380 ° C. to 420 ° C. and a holding time: 60 minutes to 2400 minutes (1 hour to 40 hours). Further, it is preferable that the holding time is longer as the Al content is higher.
- forced cooling such as water cooling or blast is used to increase the cooling rate (for example, 50 ° C./min or more), it is possible to suppress the precipitation of coarse precipitates. This is preferable.
- a desired plate thickness By rolling a plurality of times (multi-pass), a desired plate thickness can be obtained, and the average crystal grain size of the material can be reduced (for example, 10 ⁇ m or less), and plastic workability such as rolling and pressing can be improved.
- the rolling may be performed using known conditions, for example, heating not only the raw material but also the rolling roll, or a combination of non-preheat rolling and controlled rolling disclosed in Patent Document 1. In rolling with a small rolling reduction such as finish rolling, the rolling may be performed cold. Furthermore, when the above-described rolling is appropriately used with a lubricant, the frictional resistance during rolling can be reduced, and the material can be prevented from being seized and rolled.
- intermediate heat treatment may be performed between passes so long as the holding time in the temperature range of 150 ° C. to 300 ° C. described above is included in the total time.
- the holding temperature is set to 300 ° C. or lower.
- a preferable holding temperature is 250 ° C. or higher and 280 ° C. or lower.
- the final heat treatment (final annealing) can be performed on the rolled sheet obtained by the rolling process as described in Patent Document 1, this final heat treatment is not performed and the warm correction is performed as described above. Is preferable because of excellent plastic workability such as press working. Correction is performed by using a roll leveler or the like in which a plurality of rolls are arranged in a staggered manner as described in Patent Document 2, and heating the rolled plate to 100 to 300 ° C., preferably 150 to 280 ° C. Is mentioned. When plastic processing such as press processing is performed on the straightened plate that has been subjected to such warm correction, dynamic recrystallization occurs during the plastic processing, and the plastic workability is excellent.
- the said holding time in a correction process can be made very short by performing correction processing with respect to the raw material which became comparatively thin by rolling. For example, depending on the thickness of the material, the holding time can be set to several minutes, and further within one minute.
- the plastic working property of the material is preferably increased in a temperature range of 200 ° C. to 300 ° C.
- the time for holding the material at 200 ° C. to 300 ° C. at the time of plastic working is very short, for example, it may be within 60 seconds depending on the press working, and defects such as coarsening of precipitates as described above are substantially It is thought that it does not occur.
- the heat treatment conditions include a heating temperature: 100 ° C. to 300 ° C. and a heating time: about 5 minutes to 60 minutes. However, also in this heat treatment, a holding time in a temperature range of 150 ° C. to 300 ° C. is included in the total time.
- Total time to keep the material in a specific temperature range In order to produce the magnesium alloy material of the present invention having the above specific structure, the total time for maintaining the material in the temperature range of 150 ° C. or higher and 300 ° C. or lower in the steps from the solution forming step to obtaining the final product.
- the greatest feature is that the material is controlled to be 0.5 to 12 hours and the material is not heated to a temperature exceeding 300 ° C.
- Conventionally, for magnesium alloys with an Al content of over 7.5% by mass how much total time to keep the material in the temperature range of 150 ° C to 300 ° C in the process from solution treatment to final product It was not considered enough.
- a specific amount of fine precipitates is dispersed by controlling the holding time in the above temperature range where the precipitates are easily generated or the products are likely to grow as described above.
- the magnesium alloy material of the present invention having an existing structure can be obtained.
- the temperature range 150 ° C. or more and 280 ° C. or less
- the total time 1 hour or more and 6 hours or less
- the processing degree of each pass in the rolling process and the total processing degree of the rolling process conditions during the intermediate heat treatment, Control conditions during correction.
- the total time is preferably adjusted depending on the Al content.
- the chemical conversion treatment can be performed under known conditions by appropriately using a known chemical conversion treatment liquid.
- a known chemical conversion treatment liquid it is preferable to use a manganese phosphate / calcium-based solution which is a non-chromium treatment solution.
- the corrosion resistance can be further improved and the commercial value can be increased.
- the magnesium alloy material of sample No. 1 is a plate-like material (magnesium alloy plate) produced by a process of casting ⁇ solution treatment ⁇ rolling (warm) ⁇ correction (warm).
- the heating time of the material to be rolled and the rolling speed (roll peripheral speed) are adjusted in each pass of the rolling process so that the material is maintained in the temperature range of 150 ° C to 300 ° C.
- the total time was adjusted.
- heating exceeding 300 degreeC was not performed.
- the obtained rolled coil material was rewound and subjected to warm correction, and the obtained correction plate was wound up to produce a correction coil material.
- warm correction was performed using the strain applying means described in Patent Document 2 and heating the rolled plate to 220 ° C.
- the temperature was controlled so that the total time during which the material was kept in the temperature range of 150 ° C to 300 ° C by the straightening step was 0.5 to 12 hours.
- Analysis of the composition of the obtained straight plate (both mass%), Al: 8.79%, Zn: 0.64%, Mn: 0.18%, balance: Mg and impurities, and has a composition equivalent to AZ91 alloy It could be confirmed.
- the obtained long straight plate (coil material) was cut into an appropriate length to produce a plurality of short plate materials, and each plate material was cut appropriately to prepare test pieces for each test described later.
- Example No.100,200 As a comparative sample, a commercially available plate material: AZ91 alloy material (casting material with a thickness of 2.1 mm: sample No. 100) and AM60 alloy material (casting material with a thickness of 2.4 mm: sample No. 200) were prepared. Composition analysis of these commercially available materials (both mass%) showed that AZ91 alloy material was Al: 8.89%, Zn: 0.73%, Mn: 0.24%, balance: Mg and impurities, AM60 alloy material was Al: 6.00 %, Mn: 0.3%, balance: Mg and impurities. A plurality of plate materials of each composition were prepared and cut appropriately from each plate material to prepare test pieces for each test described below.
- the Charpy impact test was performed using a commercially available testing machine.
- a test piece (thickness: 2.1 mm to 2.5 mm) having a width of about 9 mm and a length of 75 mm to 80 mm is cut out from the plate material of each sample, and the longitudinal direction of each test piece is hammered by a testing machine hammer.
- Each test piece was attached to a testing machine so as to be orthogonal to the contact direction.
- the high-speed tensile test was performed using a commercially available testing machine capable of high-speed tension (here, Shimadzu Corporation hydraulic servo type high-speed tensile testing machine). This test was performed by cutting out the constricted test piece 10 shown in FIG. 5 from the plate material of each sample with reference to JIS Z 2201 (1998) and attaching each test piece to a testing machine. A plastic strain gauge 11 is attached to the front and back of the constricted portion of the test piece 10, and the plastic strain (permanent strain) is measured with this gauge 11, and from the intersection of the shoulder portion and the parallel portion at the center line of one surface of the test piece 10.
- the test conditions were tensile rate (target value): 10 m / sec, strain rate (target value): 1000 / sec, air atmosphere, room temperature (about 20 ° C.).
- the test piece 10 is produced so that its longitudinal direction is parallel to the rolling direction (the traveling direction of the rolled plate). By this high-speed tensile test, tensile strength (MPa), 0.2% proof stress (MPa), and elongation (MPa) were measured.
- the low speed tensile test was performed based on JIS Z 2241 (1998) using a commercially available testing machine.
- the test conditions were: tensile rate (target value): 2 mm / sec, strain rate (target value): 0.2 / sec, air atmosphere, room temperature (about 20 ° C.).
- tensile strength (MPa), 0.2% yield strength (MPa), and elongation (MPa) were measured.
- the load (stress) is measured by the load cell of the testing machine.
- Table 3 shows the magnitude relationship between the elongation, tensile strength, and 0.2% proof stress obtained from the results of the high-speed tensile test and the low-speed tensile test.
- Each sample was subjected to a corrosion resistance test to examine the corrosion resistance.
- a 5 mass% NaCl aqueous solution is prepared as a corrosive solution, and a test piece is cut out from the plate material of each sample, and the test piece is appropriately masked so that the exposed area of the test piece is 4 cm 2.
- the test piece was held for 96 hours in a state of being completely immersed in 50 mL of the above NaCl aqueous solution (held at room temperature (25 ⁇ 2 ° C.) under air conditioning).
- test piece was collected from the NaCl aqueous solution and analyzed for the elution amount of Mg ions in the NaCl aqueous solution by ICP emission spectroscopy (ICP-AES). Then, the value obtained by dividing the determined amount of Mg ions by the exposed area was defined as corrosion weight loss ( ⁇ g / cm 2 ). The results are shown in Table 1.
- each of the AZ91 wrought materials of sample No. 1 made of a magnesium alloy containing Al in excess of 7.5% by mass and subjected to rolling and controlling the thermal history during production is Charpy. It can be seen that the impact value is 30 J / cm 2 or more, and further 40 J / cm 2 or more, and the impact value is very high. It can also be seen that the AZ91 wrought material of sample No. 1 has a larger Charpy impact value than the AM60 cast material of sample No. 200. Here, in the Charpy impact test, generally, the impact value until the test piece breaks (breaks) is measured. However, in the case of AZ91 wrought material of sample No.
- Table 1 shows the maximum impact value that did not fall off. From this, the AZ91 wrought material of sample No. 1 has an impact value equal to or greater than the values shown in Table 1, and is expected to be very excellent in impact resistance.
- the AZ91 cast material of Sample No. 100 has the same component as Sample No. 1, but has a small Charpy impact value of less than 30 J / cm 2 . From this, it can be seen that even with similar components, those having greatly different impact values depending on the production method can be obtained.
- the AZ91 wrought material of sample No. 1 is excellent in all the properties of elongation, tensile strength, and 0.2% proof stress in the high-speed tensile test. Furthermore, all of the AZ91 wrought material of sample No. 1 has the AZ91 cast material and sample No. of sample No. 100 for any of the properties of elongation, tensile strength, and 0.2% proof stress in the high-speed tensile test. It can be seen that it has a higher value than 200 AM60 castings. Thus, it can be seen that the AZ91 wrought material of sample No. 1 has high strength and high toughness when subjected to a high-speed tensile test.
- the AZ91 wrought material of sample No. 1 has a large absolute value of the average value of elongation, tensile strength, and 0.2% proof stress in the high-speed tensile test. It can be seen that the characteristics also have little variation. That is, it can be seen that the AZ91 wrought material of sample No. 1 has a uniform characteristic while being a long coil material.
- the AZ91 cast material of sample No. 100 and the AM60 cast material of sample No. 200 have almost no difference in elongation in the high-speed tensile test and the low-speed tensile test.
- the AZ91 wrought material of sample No. 1 has a very large difference between the elongation (average value) in the high-speed tensile test: EL gh and the elongation in the low-speed tensile test: EL low .
- the elongation EL gh is 1.3 ⁇ EL low or more (here, about twice).
- AZ91 expanded material of sample No. 1 was excellent in impact resistance was because it had a structure in which precipitates such as fine intermetallic compounds were uniformly dispersed, it is conceivable that. The metal structure will be described later.
- the AZ91 wrought material of sample No. 1 is excellent in corrosion resistance even if it is not subjected to anticorrosion treatment such as chemical conversion treatment.
- the AZ91 wrought material of sample No. 1 has the same components (element content) as the AZ91 cast material of sample No. 100, but has better corrosion resistance than the AZ91 cast material of sample No. 100. I understand.
- One of the reasons why the corrosion resistance is excellent is that the specific structure is included.
- a magnesium alloy plate was prepared as a base material, a chemical conversion treatment was performed on the surface of the base material to prepare a magnesium alloy member having an anticorrosion layer, and the metal structure of the base material, the form of the anticorrosion layer, and the corrosion resistance were examined.
- Example No.1 The magnesium alloy member of sample No. 1 is manufactured by the steps of casting ⁇ solution treatment ⁇ rolling (warm) ⁇ correction (warm) ⁇ polishing ⁇ corrosion protection layer formation.
- the basic manufacturing process and manufacturing conditions of the magnesium alloy plate are the same as in Test Example 1 described above, and the difference from the magnesium alloy material produced in Test Example 1 is that in Test Example 2, sheet material is used instead of coil material. The point which produced and the point which formed the anti-corrosion layer in this sheet
- the heating time of the material to be rolled and the rolling speed (roll peripheral speed) are adjusted in each pass of the rolling process so that the material is maintained in the temperature range of 150 ° C to 300 ° C.
- the total time was set to 3 hours.
- the obtained rolled plate was warm-corrected in a state heated to 220 ° C. to prepare a corrected plate.
- Warm correction was performed using the strain applying means described in Patent Document 2.
- the time during which the material is maintained in the temperature range of 150 ° C. to 300 ° C. is as short as several minutes.
- the obtained correction plate is further subjected to wet belt type polishing using a # 600 polishing belt, the surface of the correction plate is smoothed by polishing, and a polishing plate (hereinafter sometimes referred to as a sheet material) is obtained. Produced.
- the obtained magnesium alloy member is designated as sample No. 1.
- Example No.10 Prepare the same cast material (but thickness 4.2mm) as the sample No.1 mentioned above, and after rolling under the following conditions, do not correct (warm), replace with correct (warm) What was heat-treated at 320 ° C. for 30 minutes was produced. The heat-treated plate was polished in the same manner as in Sample No. 1, and then an anticorrosion layer was formed. The obtained magnesium alloy member is designated as sample No. 10.
- Example No.110 A wrought material (thickness: 0.6 mm plate) made of a commercially available AZ31 alloy was prepared, polished in the same manner as Sample No. 1, and then an anticorrosion layer was formed. The obtained magnesium alloy member is designated as sample No. 110.
- Example No.120 A cast material (thickness: 0.6 mm plate) made of a commercially available AZ91 alloy was prepared, polished in the same manner as Sample No. 1, and then an anticorrosion layer was formed. The obtained magnesium alloy member is designated as sample No. 120.
- Sample No. 1 base material (corrected plate here), sample No. 10 base material (here heat treatment plate) prepared as described above, AZ31 alloy wrought material of sample No. 110 prepared On the other hand, the metallographic structure was observed as follows and the precipitates were examined.
- FIG. 6 (I) shows an observation image of sample No. 1
- FIG. 6 (II) shows an observation image of sample No. 110.
- a light gray (white) small granular body is a precipitate.
- the ratio of the total area of the precipitate particles to the cross section was determined as follows. As described above, each of the base material and the wrought material has five cross sections, and arbitrarily has three fields of view (here, a region of 22.7 ⁇ m ⁇ 17 ⁇ m) from the observation image of each cross section. For each observation field, calculate the total area by examining the area of all the precipitate particles existing in one observation field, and calculate the total area in the observation field with respect to the area of one observation field (here 385.9 ⁇ m 2 ). Ratio of total area of all particles: (total area of particles) / (area of observation field) is obtained, and this ratio is defined as the area ratio of the observation field. Table 4 shows the average area ratios of 15 observation fields for each of the base material and the wrought material.
- the average particle size of the precipitate particles with respect to the cross section was determined as follows. For each observation field, create a histogram of particle diameters by calculating the diameter of the equivalent area circle of the area of each particle present in one observation field, and from all the particles in the observation field, The particle diameter of the particles reaching 50% of the total area of the particles, that is, 50% particle diameter (area) is defined as the average particle diameter of the observation field. Table 4 shows the average of the average particle diameters of 15 observation fields for each of the base material and the wrought material.
- the area and diameter of the particles can be easily calculated by using a commercially available image processing apparatus. Further, when the precipitate was examined by EDS (Energy Dispersive X-ray Spectroscopy), it was an intermetallic compound containing Al or Mg such as Mg 17 Al 12 . The presence of the intermetallic compound particles can also be determined by examining the composition and structure using X-ray diffraction or the like.
- each sample (magnesium alloy member) obtained was arbitrarily cut in the plate thickness direction to take a cross section, and in that cross section, the anticorrosion layer formed by chemical conversion treatment was observed with a transmission electron microscope (TEM).
- FIG. 7 (I) shows an observation image of sample No. 1 (250,000 times)
- FIG. 7 (II) shows an observation image of sample No. 110 (100,000 times).
- the upper black region and the upper white region in FIG. 7 (II) are protective layers formed when taking a cross section.
- the median value and variation when the observed image of the anticorrosion layer was expressed in 256 gray scales (in this case, the intermediate value method) were examined (n 1).
- the results are shown in Table 4.
- the median and variation of the gray scale can be easily obtained by using a commercially available image processing apparatus. When the variation value is small, the pores are small and dense, and when the variation value is large, the pores are many and porous.
- the thickness of the anticorrosion layer (here, any five points of the observed image were selected and the average thickness of the five points) was examined using the observed images of the samples. The results are shown in Table 4.
- each sample obtained was subjected to a corrosion resistance test to investigate the corrosion resistance.
- the corrosion resistance test was performed according to JIS Z 2371 (2000) (salt water spray time: 96 hours, 35 ° C.), and the amount of change in weight (loss of corrosion) before and after salt water spray was measured. Then, the change amount ⁇ a 0.6 mg / cm 2 greater, 0.6 mg / cm 2 or less ⁇ , was evaluated less than 0.4 mg / cm 2 ⁇ with.
- Table 4 The results are shown in Table 4.
- the total time during which the material is maintained in the temperature range of 150 ° C to 300 ° C is set to a specific range, and heating above 300 ° C is not performed.
- FIG. 6 (I) it can be seen that a magnesium alloy plate (sample No. 1 substrate) having a structure in which fine intermetallic compound particles are dispersed is obtained. More specifically, in this base material, the average particle size of the intermetallic compound particles satisfies 0.05 ⁇ m to 1 ⁇ m, and the ratio of the total area of the intermetallic compound particles satisfies 1% to 20%.
- the anticorrosion layer provided on the sample No. 1 substrate is formed on the surface side with a relatively thick lower layer formed on the substrate side in the film thickness direction as shown in FIG. It can be seen that it has a two-layer structure with a relatively thin surface layer.
- the lower layer has a lower gradation (median) than the surface layer, has a large variation value, and is porous, and the surface layer has a higher gradation, a smaller variation value, and is denser than the lower layer. I understand.
- the phosphoric acid compound of manganese and calcium was the main component, and the lower layer on the substrate side had a content ratio of Al rather than the surface layer The surface layer had a higher content of manganese and calcium than the lower layer.
- Sample No. 1 having the above configuration is excellent in corrosion resistance as shown in Table 4.
- Sample No. 110 using the AZ31 alloy wrought material has very few precipitates as shown in FIG. 6 (II). Further, as shown in FIG. 7 (II), the anticorrosion layer is porous and very thick. As shown in Table 4, it can be seen that Sample No. 110 is inferior in corrosion resistance. The reason for this is that the dense surface layer like sample No. 1 does not exist in the anticorrosion layer, it is porous, and it is easy to penetrate the corrosive liquid due to the occurrence of cracks due to the thick film. In addition, it is thought that this is because the Al content (solid solution amount) of the substrate and the presence of intermetallic compounds are small.
- Sample No. 120 using the cast material of AZ91 alloy, the anticorrosion layer was more porous than the surface layer of Sample No. 1, and was thicker than Sample No. 1. It can also be seen that Sample No. 120 is inferior in corrosion resistance to Sample No. 1. The reason for this is thought to be that the corrosive liquid easily penetrates due to the occurrence of cracks due to the thick film.
- the total content time of the magnesium alloy with Al content exceeding 7.5% by mass and maintained in the temperature range of 150 ° C to 300 ° C in the manufacturing process after solution treatment is 0.5 hours to 12 hours.
- a magnesium alloy material without heating above 300 ° C. it has a structure in which precipitates such as fine intermetallic compounds are uniformly dispersed as described above.
- this magnesium alloy material is excellent in impact resistance as described in Test Example 1.
- the magnesium alloy member which is excellent in corrosion resistance is obtained when this magnesium alloy material is used as a base material and the base material is subjected to chemical conversion treatment.
- the structure was observed in the same manner for the AZ91 wrought material of sample No. 1 produced in Test Example 1, and as in the sheet material of Sample No. 1 produced in Test Example 2, a fine intermetallic compound was formed.
- the precipitate had a dispersed structure.
- the average particle diameter of the particles was 0.1 ⁇ m (100 nm), and the ratio of the total area of the precipitate particles was 6%.
- the above-described embodiment can be appropriately changed without departing from the gist of the present invention, and is not limited to the above-described configuration.
- the composition of the magnesium alloy (particularly the Al content), the thickness and shape of the magnesium alloy material, the constituent material of the anticorrosion layer, and the like can be appropriately changed.
- the magnesium alloy material of the present invention is a component that is desired to have excellent impact resistance, typically automobile parts such as bumpers, parts of various electric devices, for example, portable and small casings of electric devices, It can be suitably used as a constituent material for parts in various fields where high strength is desired.
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Abstract
Description
[マグネシウム合金材]
(組成)
本発明マグネシウム合金材を構成するマグネシウム合金は、Mgに添加元素を含有した種々の組成のもの(残部:Mg及び不純物、Mg:50質量%以上)が挙げられる。特に、本発明では、添加元素に少なくともAlを7.5質量%超含有するMg-Al系合金とする。Alを7.5質量%超含有することで、マグネシウム合金自体の強度、耐塑性変形性といった機械的特性を高められる上に、耐食性にも優れる。Al量が多いほど、強度などの機械的特性や耐食性に優れる傾向にあるが、12質量%を超えると塑性加工性の低下を招き、圧延時などに素材を高温に加熱する必要があるため、Alの含有量は、12質量%以下が好ましい。
上記マグネシウム合金は、平均粒径が0.05μm~1μmといった微細な析出物が分散した組織を有し、マグネシウム合金材の断面をとったとき、マグネシウム合金材を100面積%とするとき、上記析出物が1面積%~20面積%存在する。上記析出物は、マグネシウム合金中の添加元素を含有するもの、代表的にはMgやAlを含む金属間化合物、より具体的にはMg17Al12からなるもの(Mg17Al12に限定されない)が挙げられる。平均粒径が0.05μm以上、かつ析出物の含有量が1面積%以上であることで、上記マグネシウム合金中に析出物が十分に存在して、これら析出物の分散強化により、優れた耐衝撃性を有することができる。析出物の平均粒径が1μm以下、及び析出物の含有量が20面積%以下であることで、上記マグネシウム合金中に析出物が過剰に存在したり、粗大な析出物が存在せず、Alの固溶量の低下を抑制して、強度に優れる。より好ましい平均粒径は、0.1μm以上0.5μm以下、より好ましい析出物の含有量は、3面積%以上15面積%以下、更に12面積%以下、とりわけ5面積%以上10面積%以下である。
本発明マグネシウム合金材は、代表的には、矩形状の板状材(マグネシウム合金板)が挙げられ、矩形の他、円形状など種々の形状をとり得る。この板状材は、連続する長尺材を巻き取ったコイル材、所定の長さ・形状の短尺材といった形態をとり得る。また、この板状材は、ボスなどが接合されていたり、表裏に貫通する孔などを有する形態とすることができる。更に、この板状材は、製造工程によっても種々の形態をとり得る。例えば、圧延板、圧延板に後述する熱処理や矯正を施した熱処理板や矯正板、上記圧延板や熱処理板、矯正板に研磨を施した研磨板などの形態が挙げられる。その他、本発明マグネシウム合金材は、上記板状材に、曲げ加工や絞り加工といったプレス加工などの塑性加工を施した成形体が挙げられる。所望の用途に応じて、マグネシウム合金材の形態、大きさ(面積)や厚さを選択するとよい。特に、厚さが2.0mm以下、更に1.5mm以下、とりわけ1mm以下であると、薄型、軽量の部品(代表的には筐体や自動車部品)に好適に利用することができる。
本発明マグネシウム合金材は、シャルピー衝撃値、高速引張試験における伸び、引張強さが上述のようにAM60合金と同等以上であることを最大の特徴とする。特に、本発明マグネシウム合金材は、後述する試験例に示すように、シャルピー衝撃試験を行った場合、即ち、高速で応力を受けた場合、試験片が折損(破断)せず、屈曲する。このように本発明マグネシウム合金材は、衝撃を受けた際、十分に塑性変形して、衝撃時のエネルギーを変形により吸収できることから、例えば、シャーシやバンパーといった自動車部品の構成材料に利用された場合、自動車内の乗員の保護に寄与することができると期待される。
本発明マグネシウム合金材は、その表面に、化成処理や陽極酸化処理といった表面処理により形成された防食層を具えるマグネシウム合金部材とすることができる。このマグネシウム合金部材は、上述のように耐食性にも優れる本発明マグネシウム合金材に加えて防食層をも具えることで、耐食性に更に優れる。本発明者らが調べたところ、上記特定の組織を有するマグネシウム合金材に化成処理を施した場合、防食層が特定の構造(二層構造)を有することがある、との知見を得た。そして、この特定の構造の防食層を有するマグネシウム合金部材は、耐食性に非常に優れていた。上記防食層の具体的な構造は、上記マグネシウム合金材側に形成された下層と、上記下層の上に形成された表面層とを具える二層構造である。上記表面層は、上記下層よりも緻密であり、この下層は、ポーラス(多孔質)な層である。また、この防食層は、非常に薄く、二層構造の防食層の合計厚さが50nm以上300nm以下(下層が厚さの60%~75%程度)である。
上記特定の組織を有する本発明マグネシウム合金材が板状材である場合、例えば、以下の各工程を具えるマグネシウム合金板の製造方法により、製造することができる。
準備工程:Alを7.5質量%超含有するマグネシウム合金からなり、連続鋳造法で製造した鋳造板を準備する工程。
溶体化工程:上記鋳造板に350℃以上の温度で溶体化処理を施して、固溶板を製造する工程。
圧延工程:上記固溶板に温間圧延を施し、圧延板を製造する工程。
特に、溶体化工程以降の製造工程において、加工対象である素材板(代表的には圧延板)を150℃以上300℃以下の温度域に保持する総合計時間を0.5時間以上12時間以内とすると共に、300℃超の温度に加熱しないように、上記素材板の熱履歴を制御する。
(準備工程)
鋳造板は、双ロール法といった連続鋳造法、特に、WO/2006/003899に記載の鋳造方法で製造した鋳造板を利用することが好ましい。連続鋳造法は、急冷凝固が可能であるため、酸化物や偏析などを低減でき、割れの起点になり得る10μm超といった粗大な晶析出物の生成を抑制できる。従って、圧延性に優れる鋳造板が得られる。鋳造板の大きさは特に問わないが、厚過ぎると偏析が生じ易いため、10mm以下、特に5mm以下が好ましい。特に、長尺な鋳造板を巻き取った鋳造コイル材を作製する場合、素材における巻き取り直前の箇所を150℃以上に加熱した状態で巻き取ると、巻き取り径が小さい場合でも、割れなどが生じることなく巻き取ることができる。巻き取り径が大きい場合は、冷間で巻き取ってもよい。
上記鋳造板に溶体化処理を施して、組成を均質化すると共に、Alといった元素を固溶させた固溶板を製造する。溶体化処理は、保持温度を350℃以上、特に、保持温度:380℃~420℃、保持時間:60分~2400分(1時間~40時間)とすることが好ましい。また、保持時間は、Alの含有量が高いほど長くすることが好ましい。更に、上記保持時間からの冷却工程において、水冷や衝風といった強制冷却などを利用して、冷却速度を速めると(例えば、50℃/min以上)、粗大な析出物の析出を抑制することができて好ましい。
上記固溶板に圧延を施すにあたり、素材(固溶板や圧延途中の板)を加熱することで塑性加工性を高められる。従って、少なくとも1パスは温間圧延を施す。但し、素材の加熱温度が高過ぎると、150℃~300℃の温度域の保持時間が過度に長くなり、上述のように析出物の過度な成長や過度の析出を招いたり、素材の焼き付きが発生したり、素材の結晶粒が粗大化して圧延後の板の機械的特性が低下したりする。そのため、圧延工程において素材の加熱温度も300℃以下とする。特に、150℃以上280℃以下が好ましい。複数回(多パス)の圧延を施すことで、所望の板厚にできると共に、素材の平均結晶粒径を小さくしたり(例えば、10μm以下)、圧延やプレス加工といった塑性加工性を高められる。圧延は、公知の条件、例えば、素材だけでなく圧延ロールも加熱したり、特許文献1に開示されるノンプレヒート圧延や制御圧延などを組み合わせて利用してもよい。また、仕上げ圧延などで圧下率が小さい圧延では、冷間で圧延を施してもよい。更に、上記圧延は、潤滑剤を適宜利用すると、圧延時の摩擦抵抗を低減でき、素材の焼き付きなどを防止して、圧延を施し易い。
上記圧延工程により得られた圧延板に、特許文献1に記載されるように最終熱処理(最終焼鈍)を施すことができるが、この最終熱処理を施さず、上述のように温間矯正を施す方がプレス加工といった塑性加工性に優れて好ましい。矯正は、特許文献2に記載されるような複数のロールが千鳥状に配置されたロールレベラなどを用い、圧延板を100℃~300℃、好ましくは150℃以上280℃以下に加熱して行うことが挙げられる。このような温間矯正を行った矯正板にプレス加工といった塑性加工を施すと、塑性加工時に動的再結晶化が生じることで、塑性加工性に優れる。なお、圧延により比較的薄くなった素材に対して矯正加工を施すことで、矯正工程における上記保持時間を非常に短くすることができる。例えば、素材の厚さによっては上記保持時間を数分程度、更に1分以内とすることができる。
上記圧延板や、上記圧延板に上記最終熱処理を施した熱処理板、上記圧延板に上記矯正を施した矯正板、上記圧延板・熱処理板・矯正板のいずれかに研磨(好ましくは湿式研磨)を施した研磨板にプレス加工といった塑性加工を施す場合、200℃~300℃の温度域で行うと、素材の塑性加工性を高められて好ましい。塑性加工時において素材を上記200℃~300℃に保持する時間は、非常に短く、例えば、プレス加工によっては60秒以内の場合があり、上述したような析出物の粗大化などの不具合は実質的に生じないと考えられる。
上記特定の組織を有する本発明マグネシウム合金材を製造するには、上記溶体化工程以降、最終製品を得るまでの工程において、素材を150℃以上300℃以下の温度域に保持する総合計時間が0.5時間~12時間となるように制御すると共に、素材を300℃超の温度に加熱しないことを最大の特徴とする。従来、Alの含有量が7.5質量%超であるマグネシウム合金に対して、溶体化処理以降、最終製品までの工程において、素材を150℃~300℃の温度域に保持する総合計時間をどの程度にするか十分に検討されていなかった。これに対して、上述のように析出物が生成され易かったり、生成物が成長し易い上記温度域の保持時間を特定の範囲に制御することで、特定量の微細な析出物が分散して存在する組織を有する本発明マグネシウム合金材を得ることができる。
化成処理は、公知の化成処理液を適宜用いて、公知の条件により行うことができる。化成処理には、ノンクロム処理液であるリン酸マンガン・カルシウム系溶液などを用いることが好ましい。
マグネシウム合金材を作製して、耐衝撃性、及び機械的特性を調べた。
試料No.1のマグネシウム合金材は、鋳造→溶体化処理→圧延(温間)→矯正(温間)という工程により作製した板状材(マグネシウム合金板)である。
(圧延条件)
加工度(圧下率):5%/パス~40%/パス
板の加熱温度:250℃~280℃
ロール温度:100℃~250℃
比較の試料として、市販の板材:AZ91合金材(厚さ2.1mmの鋳造材:試料No.100)、AM60合金材(厚さ2.4mmの鋳造材:試料No.200)を用意した。これら市販材の組成分析をしたところ(いずれも質量%)、AZ91合金材は、Al:8.89%、Zn:0.73%、Mn:0.24%、残部:Mg及び不純物、AM60合金材は、Al:6.00%、Mn:0.3%、残部:Mg及び不純物であった。各組成の板材をそれぞれ複数用意し、各板材から適宜切断して、後述する各試験の試験片を作製した。
作製した試料No.1のマグネシウム合金材(以下、AZ91展伸材と呼ぶことがある)、用意した試料No.100のAZ91鋳造材、試料No.200のAM60鋳造材に対して、シャルピー衝撃試験を行って、衝撃値を測定した。その結果を表1、及び図1に示す。
作製した試料No.1のAZ91展伸材、用意した試料No.100のAZ91鋳造材、試料No.200のAM60鋳造材に対して、高速引張試験、及び低速引張試験を行って、各試験における伸び、引張強さ、0.2%耐力を測定した。その結果を表2、及び図2~図4に示す。図2~図4において、白抜きの棒グラフは高速引張試験の結果、ハッチングを付した棒グラフは低速引張試験の結果、棒グラフ上に引かれた左右方向に延びる太線の直線は、平均値を示す。
マグネシウム合金板を作製して基材とし、この基材の表面に化成処理を施して防食層を具えるマグネシウム合金部材を作製し、基材の金属組織、防食層の形態、耐食性を調べた。
試料No.1のマグネシウム合金部材は、鋳造→溶体化処理→圧延(温間)→矯正(温間)→研磨→防食層の形成、という工程により作製する。マグネシウム合金板の基本的な製造工程、製造条件は、上記試験例1と同様であり、試験例1で作製したマグネシウム合金材と異なる点は、試験例2では、コイル材ではなく、シート材を作製した点、このシート材に防食層を形成した点である。
(圧延条件)
加工度(圧下率):5%/パス~40%/パス
板の加熱温度:250℃~280℃
ロール温度:100℃~250℃
酸エッチング:5%リン酸溶液の攪拌下、40℃,1分
脱スマット:10%KOH溶液の攪拌下、60℃,10分
表面調整:pH8に調整した炭酸水溶液の攪拌下、60℃,5分
化成処理:ミリオン化学株式会社製商品名 グラインダー MC-1000(リン酸カルシウム・マンガン皮膜化成剤)、処理液温度35℃,浸漬時間60秒
乾燥:120℃,20分
上述した試料No.1と同様の鋳造材(但し、厚さ4.2mm)を用意し、以下の条件で圧延を行った後、矯正(温間)を行わず、矯正(温間)に代えて320℃×30分の熱処理を行ったものを作製した。この熱処理板に、試料No.1と同様にして研磨した後、防食層の形成を行った。得られたマグネシウム合金部材を試料No.10とする。
[粗圧延] 厚さ4.2mm→1mm
加工度(圧下率):20%/パス~35%/パス
板の加熱温度:300℃~380℃
ロール温度:180℃
[仕上げ圧延] 厚さ1mm→0.6mm
加工度(圧下率):平均7%/パス
板の加熱温度:220℃
ロール温度:170℃
なお、試料No.10において溶体化処理以降の150℃~300℃の温度域に保持した総合計時間は、15時間である。
市販のAZ31合金からなる展伸材(厚さ:0.6mmの板)を準備し、試料No.1と同様にして研磨を施した後、防食層の形成を行った。得られたマグネシウム合金部材を試料No.110とする。
市販のAZ91合金からなる鋳造材(厚さ:0.6mmの板)を準備し、試料No.1と同様にして研磨を施した後、防食層の形成を行った。得られたマグネシウム合金部材を試料No.120とする。
Claims (6)
- Alを7.5質量%超含有するマグネシウム合金からなるマグネシウム合金材であって、
シャルピー衝撃値が30J/cm2以上であることを特徴とするマグネシウム合金材。 - 引張速度が10m/secでの高速引張試験における伸びが10%以上であることを特徴とする請求項1に記載のマグネシウム合金材。
- 引張速度が10m/secでの高速引張試験における引張強さが300MPa以上であることを特徴とする請求項1又は2に記載のマグネシウム合金材。
- 引張速度が10m/secでの高速引張試験における伸びELhgが、引張速度が2mm/secでの低速引張試験における伸びELlowの1.3倍以上であることを特徴とする請求項1~3のいずれか1項に記載のマグネシウム合金材。
- 前記マグネシウム合金中に、析出物の粒子が分散して存在しており、
前記析出物の粒子の平均粒径が0.05μm以上1μm以下であり、
前記マグネシウム合金材の断面において、前記析出物の粒子の合計面積の割合が1%以上20%以下であることを特徴とする請求項1~4のいずれか1項に記載のマグネシウム合金材。 - 前記析出物の粒子は、Al及びMgの少なくとも一方を含む金属間化合物から構成される粒子を含むことを特徴とする請求項5に記載のマグネシウム合金材。
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TWI515303B (zh) * | 2010-12-28 | 2016-01-01 | 住友電氣工業股份有限公司 | 鎂合金材料 |
JP6048217B2 (ja) * | 2013-02-28 | 2016-12-21 | セイコーエプソン株式会社 | マグネシウム基合金粉末およびマグネシウム基合金成形体 |
JP6048216B2 (ja) | 2013-02-28 | 2016-12-21 | セイコーエプソン株式会社 | マグネシウム基合金粉末およびマグネシウム基合金成形体 |
JP6465338B2 (ja) * | 2014-10-15 | 2019-02-06 | 住友電気工業株式会社 | マグネシウム合金、マグネシウム合金板、マグネシウム合金部材、及びマグネシウム合金の製造方法 |
JPWO2018109947A1 (ja) * | 2016-12-16 | 2019-06-24 | 三協立山株式会社 | マグネシウム合金の製造方法およびマグネシウム合金 |
KR101889018B1 (ko) | 2016-12-23 | 2018-09-20 | 주식회사 포스코 | 마그네슘 합금 판재 및 이의 제조방법 |
KR102356979B1 (ko) * | 2017-01-18 | 2022-01-27 | 아르코닉 테크놀로지스 엘엘씨 | 접착제 접합용 7xxx 알루미늄 합금의 제조 방법, 및 이와 관련된 제품 |
US11268173B2 (en) | 2017-11-17 | 2022-03-08 | Sumitomo Electric Industries, Ltd. | Magnesium alloy and magnesium alloy member |
CN110408827A (zh) * | 2018-04-28 | 2019-11-05 | 澳洋集团有限公司 | 一种铝-镁合金及其制备方法 |
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- 2010-12-06 BR BR112012013855A patent/BR112012013855A2/pt not_active IP Right Cessation
- 2010-12-06 KR KR1020127014877A patent/KR101463319B1/ko active IP Right Grant
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- 2010-12-06 RU RU2012129180/02A patent/RU2516128C2/ru active
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- 2010-12-06 CN CN201080056199XA patent/CN102652180A/zh active Pending
- 2010-12-06 WO PCT/JP2010/071849 patent/WO2011071024A1/ja active Application Filing
- 2010-12-06 EP EP10835944.9A patent/EP2511392B1/en not_active Not-in-force
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Also Published As
Publication number | Publication date |
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EP2511392A4 (en) | 2017-08-09 |
EP2511392B1 (en) | 2018-11-28 |
JP2011140712A (ja) | 2011-07-21 |
TWI470087B (zh) | 2015-01-21 |
US20120282131A1 (en) | 2012-11-08 |
CN104250697A (zh) | 2014-12-31 |
CN104250697B (zh) | 2017-10-27 |
RU2012129180A (ru) | 2014-01-20 |
EP2511392A1 (en) | 2012-10-17 |
JP5522400B2 (ja) | 2014-06-18 |
CN102652180A (zh) | 2012-08-29 |
KR20120081628A (ko) | 2012-07-19 |
US8906294B2 (en) | 2014-12-09 |
KR101463319B1 (ko) | 2014-11-18 |
RU2516128C2 (ru) | 2014-05-20 |
TW201134951A (en) | 2011-10-16 |
BR112012013855A2 (pt) | 2018-05-29 |
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