JP5557121B2 - Magnesium alloy - Google Patents
Magnesium alloy Download PDFInfo
- Publication number
- JP5557121B2 JP5557121B2 JP2012505620A JP2012505620A JP5557121B2 JP 5557121 B2 JP5557121 B2 JP 5557121B2 JP 2012505620 A JP2012505620 A JP 2012505620A JP 2012505620 A JP2012505620 A JP 2012505620A JP 5557121 B2 JP5557121 B2 JP 5557121B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium alloy
- crystal grains
- grains
- magnesium
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 61
- 239000013078 crystal Substances 0.000 claims description 57
- 238000005096 rolling process Methods 0.000 claims description 36
- 239000011777 magnesium Substances 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 44
- 239000010419 fine particle Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002245 particle Substances 0.000 description 19
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 238000012669 compression test Methods 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000003754 machining Methods 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000013079 quasicrystal Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 239000012770 industrial material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000000304 warm extrusion Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
- Metal Rolling (AREA)
Description
本発明は、マグネシウムを主成分とするマクネシウム合金に関する。 The present invention relates to a magnesium alloy containing magnesium as a main component.
マグネシウム合金は、高強度のものが近年開発され、アルミニウム合金に変わる新素材として、自動車、航空機などの構成材料への応用が注目されている。 Magnesium alloys have been developed in recent years with high strength, and as a new material that replaces aluminum alloys, application to constituent materials such as automobiles and aircraft has been attracting attention.
しかし、そのような工業用材料として使用するためには、マグネシウム合金には加工性が悪いという問題があり、この問題を改善するために開発が勢力的に行われているが、未だ十分な解決は得られていない。 However, in order to use it as such an industrial material, there is a problem that the magnesium alloy has poor workability, and development has been carried out to improve this problem, but it is still a sufficient solution Is not obtained.
たとえば、延性を向上させるための方策として押出加工材とすることが検討されてもいるが、この場合、圧縮強度を向上させるのが難しく、また、圧縮降伏応力と引張降伏応力の比である変形異方性比が強くなり、軽量構造材料としての利用が困難となるという問題がある。 For example, although it has been studied to use an extruded material as a measure for improving ductility, in this case, it is difficult to improve the compressive strength, and the deformation is a ratio of the compressive yield stress to the tensile yield stress. There is a problem that the anisotropy ratio becomes strong, making it difficult to use as a lightweight structural material.
一方、本出願人は、下記特許文献１において、結晶構造を制御することによって、高強度でありながら十分な加工性を有するマグネシウム合金が提供可能であることを明らかにしたが、実用的にはさらなる強度および延性の向上が望まれている。 On the other hand, in the following Patent Document 1, the present applicant has clarified that it is possible to provide a magnesium alloy having a high strength but sufficient workability by controlling the crystal structure. Further improvements in strength and ductility are desired.
本発明は、上記のとおりの実情に鑑み、従来では不可能とされていた強度および延性を実現したマグネシウム合金を提供することを課題としている。 In view of the actual situation as described above, an object of the present invention is to provide a magnesium alloy that realizes strength and ductility that have been impossible in the past.
上記の課題を解決するために、本発明のマグネシウム合金は、化学組成がＭｇ−Ａmass％Ｚｎ−Ｂmass％Ｚ（Ｍｇ：マグネシウム、Ｚｎ：亜鉛、Ｚ：他の金属元素）で表され、不可避的不純物を含有するマグネシウム合金であって、６≦Ａ＜１０のとき、Ｚは、Ａｌ、Ｚｒ、Ｃａ、Ｓｎ、Ｌｉ、Ａｇまたは希土類元素のうちのいずれか一種であり、０＜Ｂ＜１０であり、０＜Ａ＜６のとき、Ｚは、Ａｌであり、６≦Ｂ＜１０であり、溝ロール圧延により断面減少率が９０％以上である加工ひずみが導入され、方位差角が１５度以上の粒界である大傾角粒界を有し、この大傾角粒界に囲まれた結晶粒の内部が亜結晶粒から形成され、亜結晶粒の内部に、平均粒径が１０nm以上１μm以下の微細な粒子が分散していることを特徴としている。 In order to solve the above problems, the magnesium alloy of the present invention has a chemical composition represented by Mg—Amass% Zn—Bmass% Z (Mg: magnesium, Zn: zinc, Z: other metal elements), and is unavoidable. A magnesium alloy containing impurities, and when 6 ≦ A <10, Z is any one of Al, Zr, Ca, Sn, Li, Ag, or a rare earth element, and 0 <B <10 Yes, when 0 <A <6, Z is Al, 6 ≦ B <10, and processing strain with a cross-section reduction rate of 90% or more is introduced by groove roll rolling, and the misorientation angle is 15 degrees. It has the above-mentioned large-angle grain boundary, and the inside of the crystal grain surrounded by this large-angle grain boundary is formed of sub-crystal grains, and the average grain size is 10 nm or more and 1 μm inside the sub-crystal grains. It is characterized in that the following fine particles are dispersed.
本発明のマグネシウム合金においては、結晶粒の平均粒径が５μm以下で、亜結晶粒の平均粒径が１．５μm以下であることが好ましい。 In the magnesium alloy of the present invention, the average grain size of crystal grains is preferably 5 μm or less, and the average grain size of sub-crystal grains is preferably 1.5 μm or less.
また、本発明のマグネシウム合金においては、粒径が５μm以下の結晶粒が、全結晶粒の７０％以上を占めることが好ましい。 In the magnesium alloy of the present invention, it is preferable that crystal grains having a grain size of 5 μm or less occupy 70% or more of all crystal grains.
また、本発明のマグネシウム合金においては、微細な粒子の亜結晶粒における密度が１５％以下（ただし、０％を含まない）であることが好ましい。 Moreover, in the magnesium alloy of this invention, it is preferable that the density in the subcrystal grain of a fine particle is 15% or less (however, 0% is not included).
本発明のマグネシウム合金によれば、従来では不可能とされていた強度および延性を実現することができる。 According to the magnesium alloy of the present invention, it is possible to achieve strength and ductility that were previously impossible.
本発明のマグネシウム合金の化学組成は、これまでの一般的なマグネシウム合金と同様に、マグネシウムを主成分とし、亜鉛やアルミニウムなどの金属元素が１種または２種以上添加されたものである。たとえば、亜鉛との二元系をはじめ、亜鉛とその他の金属元素との三元系や多元系などが例示される。化学組成をＭｇ−Ａmass％Ｚｎ−Ｂmass％Ｚ（Ｍｇ：マグネシウム、Ｚｎ：亜鉛、Ｚ：他の金属元素）と表す場合、０＜Ａ＜１０、０＜Ｂ＜１０とするのが好ましい。Ｚｎおよびその他の元素を１０mass％以上添加すると、後述する微細な粒子の亜結晶粒における密度が１５％を超えることになり、マグネシウム合金の作製が難しくなったり、延性が低下する要因となったりしやすい。上記化学組成において、Ｚには、Ａｌ、Ｚｒ、Ｃａ、Ｓｎ、Ｌｉ、Ａｇなどの金属元素の他、Ｙ、Ｈｏ、Ｇｄ、Ｔｂ、Ｄｙ、Ｅｒなどの希土類元素なども例示される。 The chemical composition of the magnesium alloy of the present invention is such that magnesium is the main component and one or more metal elements such as zinc and aluminum are added, as in conventional magnesium alloys. For example, a binary system with zinc, a ternary system with zinc and other metal elements, and a multi-element system are exemplified. When the chemical composition is expressed as Mg-Amass% Zn-Bmass% Z (Mg: magnesium, Zn: zinc, Z: other metal elements), 0 <A <10 and 0 <B <10 are preferable. If Zn and other elements are added in an amount of 10 mass% or more, the density of the sub-grains of fine particles described later will exceed 15%, which may make it difficult to produce a magnesium alloy or reduce ductility. Cheap. In the above chemical composition, examples of Z include metal elements such as Al, Zr, Ca, Sn, Li, and Ag, and rare earth elements such as Y, Ho, Gd, Tb, Dy, and Er.
一方、本発明のマグネシウム合金は、その結晶構造に特に特徴を有している。その結晶構造は、
１） 大傾角粒界を有する、
２） 大傾角粒界に囲まれた結晶粒、すなわち、大傾角粒の内部が亜結晶粒である、
３） 亜結晶粒の内部に、準結晶粒子や第二相析出粒子などの微細な粒子が分散している、
ことを基本としている。On the other hand, the magnesium alloy of the present invention is particularly characterized by its crystal structure. Its crystal structure is
1) has a large tilt grain boundary,
2) A crystal grain surrounded by a large-angle grain boundary, that is, the inside of the large-angle grain is a sub-crystal grain.
3) Fine particles such as quasicrystalline particles and second phase precipitated particles are dispersed inside the subcrystalline grains.
It is based on that.
「大傾角粒界」は、方位差角が１５度以上の粒界と定義される。このような大傾角粒界は、ＳＥＭ/ＥＢＳＤ(Scanning Electron Microscopy：走査型電子顕微鏡/Electron Back-Scattered Diffraction：電子線後方散乱回折)による結晶方位マッピングや透過型電子顕微鏡による方位差計測などによって確認される。 “Large-angle grain boundary” is defined as a grain boundary having a misorientation angle of 15 degrees or more. Such a large-angle grain boundary is confirmed by crystal orientation mapping by SEM / EBSD (Scanning Electron Microscopy: Electron Back-Scattered Diffraction) or orientation difference measurement by a transmission electron microscope. Is done.
この大傾角粒界に囲まれた結晶粒の平均粒径は、好ましくは５μm以下、より好ましくは、３μm以下である。また、粒径が５μm以下の結晶粒が、全結晶粒の７０％以上を占めることが好ましい。粒径が５μm以下の結晶粒が、全結晶粒の７０％以上を占めると、塑性変形時に双晶が形成しにくくなり、圧縮応力が良好となる。このため、等方変形能の両立がより可能となる。このような結晶粒は、マグネシウム母相から形成され、マグネシウム母相は、具体的には、マグネシウムと、マグネシウムに固溶する原子から構成されている。 The average grain size of the crystal grains surrounded by this large tilt grain boundary is preferably 5 μm or less, more preferably 3 μm or less. Further, it is preferable that crystal grains having a grain size of 5 μm or less occupy 70% or more of all crystal grains. When the crystal grains having a particle size of 5 μm or less occupy 70% or more of the total crystal grains, twins are hardly formed during plastic deformation, and the compressive stress is improved. For this reason, it is possible to achieve both isotropic deformability. Such crystal grains are formed from a magnesium matrix, and specifically, the magnesium matrix is composed of magnesium and atoms that dissolve in magnesium.
「亜結晶粒」は、方位差角が５度以下の粒界を有するものと定義される。この亜結晶粒の平均粒径は、１．５μm以下、好ましくは、１μm以下、より好ましくは、０．５μm以下である。亜結晶粒もまたマグネシウム母相から形成されるものであるが、上記結晶粒、すなわち、大傾角粒との違いは、隣り合う亜結晶粒との方位差が５度以下であることである。 A “subgrain” is defined as having a grain boundary with a misorientation angle of 5 degrees or less. The average grain size of the sub-crystal grains is 1.5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less. Subcrystal grains are also formed from a magnesium matrix, but the difference from the above crystal grains, that is, large-angle grains, is that the orientation difference between adjacent subcrystal grains is 5 degrees or less.
亜結晶粒の内部に分散している微細な粒子の平均粒径は、好ましくは、１０nm以上１μm以下、より好ましくは、２５nm以上５００nm以下である。平均粒径が１０nm未満であると、高強度化への寄与が小さくなりやすく、平均粒径が１μmを超えると、塑性変形中に粒子が破壊の起点となりやすく、マグネシウム合金の延性が低減する傾向が大きくなる。また、この微細な粒子の亜結晶粒における密度は、好ましくは、１５％以下、より好ましくは、１０％以下である（ただし、０％は含まない）。密度が１５％を超えると、塑性変形中に粒子が破壊の起点となりやすく、マグネシウム合金の延性が低減する傾向が大きくなる。微細な粒子の平均粒径と密度が、好ましい上限を超えると、たとえば図７に示したように、マグネシウム合金の作製中に割れやクラックなどが発生し、上記１）、２）の特徴を有する健全なマグネシウム合金を作製することが難しくなる場合がある。このような微細な粒子とマグネシウム母相の界面は、整合であっても、非整合であってもよい。整合または非整合は、微細な粒子を構成する化学組成や材料創製法によって決まる。微細な粒子は、マグネシウムに対して固溶しない原子や固溶しきれない原子が金属間化合物などとして析出したものである。また、微細な粒子には準結晶粒子が含まれる。準結晶粒子とは、マグネシウム母相と整合な界面を形成するだけでなく、結晶配列が存在しないものである。その化学組成は、Ｍｇ−Ｚｎ−ＲＥ、Ｍｇ−Ｚｎ−Ａｌなどと示される。 The average particle diameter of the fine particles dispersed in the sub-crystal grains is preferably 10 nm or more and 1 μm or less, and more preferably 25 nm or more and 500 nm or less. If the average particle size is less than 10 nm, the contribution to high strength tends to be small, and if the average particle size exceeds 1 μm, the particles tend to be the starting point of fracture during plastic deformation, and the ductility of the magnesium alloy tends to decrease. Becomes larger. Further, the density of the fine grains in the sub-crystal grains is preferably 15% or less, more preferably 10% or less (however, 0% is not included). When the density exceeds 15%, the particles are likely to become the starting point of fracture during plastic deformation, and the tendency of the ductility of the magnesium alloy to decrease increases. When the average particle size and density of the fine particles exceed the preferable upper limit, for example, as shown in FIG. 7, cracks or cracks are generated during the production of the magnesium alloy, and the characteristics 1) and 2) are provided. It may be difficult to produce a sound magnesium alloy. The interface between such fine particles and the magnesium matrix may be matched or non-matched. Matching or mismatching is determined by the chemical composition constituting the fine particles and the material creation method. Fine particles are those in which atoms that do not dissolve in magnesium or atoms that cannot completely dissolve precipitate as an intermetallic compound. The fine particles include quasicrystalline particles. The quasicrystalline particles not only form an interface consistent with the magnesium matrix but also have no crystal alignment. Its chemical composition is indicated as Mg—Zn—RE, Mg—Zn—Al, or the like.
上記のとおりの結晶構造を有する本発明のマグネシウム合金は、３３０MPa以上の引張強さを実現する。また、本発明のマグネシウム合金は、３００MPa以上の引張降伏応力（Ａ）と、２２０MPa以上の圧縮降伏応力（Ｂ）を実現し、０．７以上の降伏応力異方性比（Ｂ/Ａ）を実現する。 The magnesium alloy of the present invention having the crystal structure as described above realizes a tensile strength of 330 MPa or more. Further, the magnesium alloy of the present invention achieves a tensile yield stress (A) of 300 MPa or more and a compressive yield stress (B) of 220 MPa or more, and a yield stress anisotropy ratio (B / A) of 0.7 or more. Realize.
このように、本発明のマグネシウム合金は、従来では不可能とされていた強度および延性を実現する。このような優れた特性は、亜結晶粒の存在により結晶粒自体の変形が可能になる一方、結晶粒間の滑りが阻止されるととともに、微細な粒子の存在により転位運度が阻害されるからであると推測される。本発明のマグネシウム合金では、上記のとおりの結晶構造により、高強度化と、変形異方性の低減、すなわち、等方変形能の両立が図られている。 As described above, the magnesium alloy of the present invention achieves strength and ductility that have been impossible in the past. Such excellent properties allow the crystal grains themselves to be deformed due to the presence of sub-crystal grains, while preventing slippage between the crystal grains and inhibiting the dislocation mobility due to the presence of fine grains. It is estimated that In the magnesium alloy of the present invention, both the increase in strength and the reduction in deformation anisotropy, that is, the isotropic deformability are achieved by the crystal structure as described above.
本発明のマグネシウム合金を製造するためには、加工ひずみの導入が有効である。 In order to produce the magnesium alloy of the present invention, it is effective to introduce processing strain.
「加工ひずみ」は、所定の温度で荷重を加えて永久変形させることと定義される。このような加工ひずみの導入は、たとえば、溝ロール圧延や高押出比での押出加工、高圧下率での圧延、ＥＣＡＥ（Equal-channel-angular-extrusion：等断面積側方押出加工）のような高ひずみせん断加工などにより実現される。 “Processing strain” is defined as a permanent deformation by applying a load at a predetermined temperature. Such processing strain is introduced, for example, by groove roll rolling, extrusion at a high extrusion ratio, rolling at a high pressure ratio, ECAE (Equal-channel-angular-extrusion). Realized by high strain shearing.
溝ロール圧延は、表面に、三角形などの断面形状を有する溝が設けられた圧延ロールを用いた圧延であり、三角形の断面形状の場合、上下の圧延ロールを接触させたときに、ダイヤモンド形状の穴が形成されるという特徴を有している。本発明のマグネシウム合金の製造においては、このような溝ロール圧延は好ましい方式である。圧延ロールの溝形状については、上記ダイヤモンド形状の他、六角形形状、楕円形状などの穴を形成することができるものが例示される。圧延時の圧延ロールの周速度は、１〜５０ｍ/分の範囲が好ましく例示される。また、溝ロール圧延に際しては、あらかじめ材料を１００〜５００℃の温度範囲で５〜１２０分間熱処理しておくことが好ましい。 Groove roll rolling is rolling using a roll having a groove having a cross-sectional shape such as a triangle on the surface, and in the case of a triangular cross-sectional shape, when the upper and lower rolling rolls are brought into contact with each other, It has the feature that a hole is formed. In the production of the magnesium alloy of the present invention, such groove roll rolling is a preferred method. Examples of the groove shape of the rolling roll include those that can form holes such as a hexagonal shape and an elliptical shape in addition to the diamond shape. A range of 1 to 50 m / min is preferably exemplified as the peripheral speed of the rolling roll during rolling. Moreover, in the groove roll rolling, it is preferable to heat-treat the material in the temperature range of 100 to 500 ° C. for 5 to 120 minutes in advance.
上記のとおりの溝ロール圧延をはじめとする各種の方式による加工ひずみの導入の際には、材料が割れることのない温度で材料全体が均一になるように加熱保持し、その後、繰り返しひずみを導入することが好適である。材料の断面減少率は、加工ひずみの導入のための諸条件との関係において適宜設定することができる。つまり、上記結晶構造が形成されることを条件として断面減少率を設定することができる。たとえば、断面減少率は、９２％、９５％などと設定することができる。９０％以上の断面減少率で加工ひずみを導入することにより、良好な延性を低下させずに強度を増加させることが顕著に可能となる。ひずみを繰り返し導入する場合には、連続して行うことが好ましく、その際の単パスで導入するひずみは、総断面減少率が９０％以上となるように、たとえば、断面減少率が１０〜２０％程度のもので十分である。 When introducing processing strain by various methods including groove roll rolling as described above, heat and hold so that the entire material becomes uniform at a temperature at which the material does not break, and then repeated strain is introduced. It is preferable to do. The cross-sectional reduction rate of the material can be appropriately set in relation to various conditions for introducing processing strain. That is, the cross-sectional reduction rate can be set on condition that the crystal structure is formed. For example, the cross-section reduction rate can be set to 92%, 95%, or the like. By introducing a working strain at a cross-sectional reduction rate of 90% or more, it is possible to increase the strength without deteriorating good ductility. When the strain is repeatedly introduced, it is preferably performed continuously, and the strain introduced by a single pass at that time is, for example, a cross-sectional reduction rate of 10 to 20 so that the total cross-sectional reduction rate is 90% or more. % Is sufficient.
大傾角粒界に囲まれた結晶粒については、断面減少率を大きくするなどによって加工ひずみ導入を大きくするほど、粒径が５μm以下のものが占める割合が増大し、断面減少率が９０％以上になると、粒径５μm以下の結晶粒の占める割合は９０％以上となる。また、断面減少率が９０以上になると、結晶粒内の亜結晶粒の平均粒径が１．５μm以下となり、しかも、亜結晶粒の内部に、平均粒径が１０nm以上１μm以下の微細な粒子が、１５％以下（ただし、０％を含まない）の密度で分散する。 For crystal grains surrounded by large-angle grain boundaries, the proportion of grains with a grain size of 5 μm or less increases as the processing strain is increased by increasing the cross-section reduction rate, and the cross-section reduction rate is 90% or more. Then, the proportion of crystal grains having a grain size of 5 μm or less is 90% or more. Moreover, when the cross-section reduction rate is 90 or more, the average grain size of the sub-crystal grains in the crystal grains becomes 1.5 μm or less, and fine particles with an average grain diameter of 10 nm or more and 1 μm or less are contained inside the sub-crystal grains. Is dispersed at a density of 15% or less (excluding 0%).
このような加工ひずみの導入は、断面積の大きなものや複雑な形状を有する長尺材にも適用が可能であり、材料の大型化にも対応が可能であるため、実用的である。 The introduction of such processing strain is practical because it can be applied to a long material having a large cross-sectional area or a complicated shape, and can cope with an increase in material size.
以下、実施例を示し、本発明のマグネシウム合金についてさらに詳しく説明する。もちろん、本発明は、以下の実施例によって限定されるものではない。 Hereinafter, examples will be shown to describe the magnesium alloy of the present invention in more detail. Of course, the present invention is not limited to the following examples.
商用純マグネシウム（純度９９．９５％）に７．５質量％の亜鉛と１．７質量％のイットリウムを溶解し、鋳造して母合金を作製した。この母合金を溶体化処理した後、機械加工により直径４０ｍｍの圧延用ビレットを作製した。この圧延用ビレットを３５０℃に昇温した炉内で時間保持した後、溝ロール圧延を行った。圧延ロールの表面温度は室温とし、圧延ロールのロール周速度は３０ｍ/分とした。また、断面減少率を１パスあたり１８％とし、１９回繰り返し溝ロール圧延を行った。総断面減少率は９５％であった。 7.5 mass% zinc and 1.7 mass% yttrium were dissolved in commercial pure magnesium (purity 99.95%) and cast to prepare a master alloy. After this mother alloy was subjected to solution treatment, a billet for rolling having a diameter of 40 mm was produced by machining. The rolling billet was held in a furnace heated to 350 ° C. for a time, and then grooved rolling was performed. The surface temperature of the rolling roll was room temperature, and the roll peripheral speed of the rolling roll was 30 m / min. Moreover, the cross-section reduction rate was set to 18% per pass, and groove rolling was repeated 19 times. The total cross-section reduction rate was 95%.
得られた圧延材の微細組織を、透過型電子顕微鏡（ＴＥＭ）を用いて観察した。観察部位は、圧延方向に対して平行な断面とした。図１は、大傾角粒の内部の微細組織の例である。結晶粒界が鮮明ではなく、方位差角が小さい亜結晶粒から微細組織が形成されていることが分かる。図１図中の符号Ｓは、亜結晶粒を示している。同様の模様とコントラストで示された領域も亜結晶粒である。また、亜結晶粒の平均粒径が約１μmであることが分かる。図１図中の符号Ｉは、準結晶粒子を示し、亜結晶粒の内部に粒径１００nmの微細な粒子が分散していることが確認される。 The microstructure of the obtained rolled material was observed using a transmission electron microscope (TEM). The observation site was a cross section parallel to the rolling direction. FIG. 1 is an example of a fine structure inside a large-tilt grain. It can be seen that the fine grain structure is formed from the sub-crystal grains whose crystal grain boundaries are not clear and whose misorientation angle is small. The code | symbol S in FIG. 1 figure has shown the subcrystal grain. Regions indicated by similar patterns and contrasts are also subgrains. Moreover, it turns out that the average particle diameter of a subcrystal grain is about 1 micrometer. 1 indicates a quasicrystalline particle, and it is confirmed that fine particles having a particle diameter of 100 nm are dispersed inside the subcrystalline grains.
このような圧延材から、平行部の直径が３mm、長さ１５mmの引張試験片を、また、直径４mm、高さ８mmの圧縮試験片をそれぞれ採取した。いずれの試験片の採取方向も、圧延方向に対して平行方向とした。初期引張・圧縮ひずみ速度は、１×１０−３ ｓ−１とした。図２に室温引張により得られた公称応力−公称ひずみ曲線を示した。また、表１に機械的特性を示した。なお、降伏応力には、０．２％ひずみのオフセット値を使用した。降伏異方性比が１に近い値を示し、等方変形することが可能なマグネシウム合金が得られている。後述の比較例１と比べると、ほぼ同じ断面減少率のひずみ加工を行っているが、実施例１のマグネシウム合金は、３４％高い引張強度を示すことが分かる。また、亜結晶粒組織を有するが、微細な粒子が存在しない、後述の比較例４と比べると、降伏異方性の改善が認められる。比較例４の商用マグネシウム合金押出材は、亜鉛およびアルミニウムがすべてマグネシウムに固溶していると考えられるため、微細な粒子が析出しにくいと推定される。From such a rolled material, a tensile test piece having a parallel part diameter of 3 mm and a length of 15 mm and a compression test piece having a diameter of 4 mm and a height of 8 mm were collected. The sampling direction of any test piece was also parallel to the rolling direction. The initial tensile / compressive strain rate was 1 × 10 −3 s −1 . FIG. 2 shows a nominal stress-nominal strain curve obtained by room temperature tension. Table 1 shows the mechanical characteristics. For the yield stress, an offset value of 0.2% strain was used. A magnesium alloy having a yield anisotropy ratio close to 1 and capable of isotropic deformation is obtained. As compared with Comparative Example 1 which will be described later, strain processing with substantially the same cross-sectional reduction rate is performed, but it can be seen that the magnesium alloy of Example 1 shows a tensile strength that is 34% higher. In addition, an improvement in yield anisotropy is recognized as compared with Comparative Example 4 described later, which has a subcrystalline structure but does not have fine particles. The commercial magnesium alloy extruded material of Comparative Example 4 is presumed that fine particles are unlikely to precipitate because zinc and aluminum are all considered to be dissolved in magnesium.
商用純マグネシウム（純度９９．９５％）に８質量％の亜鉛と４質量％のアルミニウムを溶解し、鋳造して母合金を作製した。この母合金を溶体化処理した後、機械加工により直径４０mmの圧延用ビレットを作製した。その後、加工温度を２００℃にした以外は実施例１と同様にして圧延材を作製した。図３は、ＴＥＭを用いた微細組織の観察例である。図１と同様の微細組織、すなわち、亜結晶粒Ｓから形成された微細組織が確認される。また、亜結晶粒の平均結晶粒径は約０．５μmであり、亜結晶粒の内部に平均粒径が約５０nm程度の微細な粒子として準結晶粒子Ｉの分散が確認される。この圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を図２と表１に示した。実施例２のマグネシウム合金は、後述の比較例２と比べ、３７％高い引張強度を示すことが分かる。比較例２では、温間押出加工を行っているので、亜結晶粒が形成されにくく、亜結晶粒の存在割合が少なかったのではないかと推定される。また、亜結晶粒組織を有するが、微細な粒子が存在しない比較例４と比べると、６％高い引張強度を示し、微細な粒子の存在がより高強度化に寄与することが分かる。 8 mass% zinc and 4 mass% aluminum were melt | dissolved in commercial pure magnesium (purity 99.95%), and the mother alloy was produced by casting. After this mother alloy was subjected to solution treatment, a billet for rolling having a diameter of 40 mm was produced by machining. Thereafter, a rolled material was produced in the same manner as in Example 1 except that the processing temperature was 200 ° C. FIG. 3 is an example of observation of a fine structure using TEM. A fine structure similar to that of FIG. 1, that is, a fine structure formed from the subcrystalline grains S is confirmed. Further, the average crystal grain size of the sub-crystal grains is about 0.5 μm, and the dispersion of the quasi-crystal grains I is confirmed as fine particles having an average grain size of about 50 nm inside the sub-crystal grains. This rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in FIG. It can be seen that the magnesium alloy of Example 2 exhibits a 37% higher tensile strength than Comparative Example 2 described later. In Comparative Example 2, since warm extrusion is performed, it is estimated that subcrystal grains are difficult to be formed and the existence ratio of subcrystal grains is small. In addition, the tensile strength is 6% higher than that of Comparative Example 4 which has a subcrystalline structure but does not include fine particles, and it can be seen that the presence of fine particles contributes to higher strength.
商用純マグネシウム（純度９９．９５％）に６質量％の亜鉛と３質量％のアルミニウムを溶解し、鋳造して母合金を作製した。この母合金を溶体化処理した後、機械加工により直径４０mmの圧延用ビレットを作製した。その後、加工温度を２００℃にしたこと以外は実施例１と同様にして圧延材を作製した。図４は、ＴＥＭを用いた微細組織の観察例である。図１と同様の微細組織、すなわち、亜結晶粒から形成された微細組織が確認される。また、亜結晶粒の平均結晶粒径は約０．５μmであり、亜結晶粒の内部に平均粒径が約５０nm程度の微細な粒子として準結晶粒子の分散が確認される。この圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を図２と表１に示した。実施例３のマグネシウム合金は、後述の比較例３と比べ、５９％高い引張強度を示すことが分かる。また、亜結晶粒組織を有するが、微細な粒子が存在しない比較例４と比べると、７％高い引張強度を示し、微細粒子の存在がより高強度化に寄与することが分かる。 6 mass% zinc and 3 mass% aluminum were melt | dissolved in commercial pure magnesium (purity 99.95%), and the mother alloy was produced by casting. After this mother alloy was subjected to solution treatment, a billet for rolling having a diameter of 40 mm was produced by machining. Thereafter, a rolled material was produced in the same manner as in Example 1 except that the processing temperature was 200 ° C. FIG. 4 is an example of observation of a microstructure using a TEM. A fine structure similar to that shown in FIG. 1, that is, a fine structure formed from sub-crystal grains is confirmed. The average crystal grain size of the sub-crystal grains is about 0.5 μm, and the dispersion of the quasi-crystal grains is confirmed as fine particles having an average grain size of about 50 nm inside the sub-crystal grains. This rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in FIG. It can be seen that the magnesium alloy of Example 3 shows 59% higher tensile strength than Comparative Example 3 described later. Moreover, compared with the comparative example 4 which has a subcrystal grain structure but does not have fine particles, it shows a tensile strength that is 7% higher, and it can be seen that the presence of fine particles contributes to higher strength.
商用マグネシウム合金押出材（ＺＫ６０：６質量％の亜鉛と０．５質量％のジルコニウムを添加）を使用し、機械加工により、直径４０mmの圧延用ビレットを作製した。その後、加工温度を２００℃にしたこと以外は実施例１と同様にして圧延材を作製した。この圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を表１に示した。実施例４のマグネシウム合金は、降伏異方性比が１に近い値を示し、等方変形することが可能なマグネシウム合金が得られている。また、比較例４と比べると、５％高い引張強度を示し、微細な粒子の存在がより高強度化に寄与することが分かる。なお、微細な粒子は、マグネシウム母相と非整合界面を形成し、Ｍｇ２Ｚｎからなる第二相析出粒子である。A commercial magnesium alloy extruded material (ZK60: 6 mass% zinc and 0.5 mass% zirconium added) was used, and a billet for rolling having a diameter of 40 mm was produced by machining. Thereafter, a rolled material was produced in the same manner as in Example 1 except that the processing temperature was 200 ° C. This rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in Table 1. The magnesium alloy of Example 4 has a yield anisotropy ratio close to 1, and a magnesium alloy capable of isotropic deformation is obtained. Moreover, compared with the comparative example 4, 5% higher tensile strength is shown, and it can be seen that the presence of fine particles contributes to higher strength. The fine particles are second-phase precipitated particles that form an inconsistent interface with the magnesium matrix and are composed of Mg 2 Zn.
実施例２と同じ材料を使用し、加工温度を３００℃としたことと、溝ロール圧延を１５回繰り返し、総断面減少率を９２％にしたこと以外は実施例１と同様にして圧延材を作製した。得られた圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を表１に示した。総断面減少率が同じであるが、微細な粒子が存在しない比較例５と比べると、微細な粒子である準結晶粒子が、亜結晶粒の内部に分散している実施例５のマグネシウム合金は、降伏異方性の改善が認められる。比較例５の商用マグネシウム合金押出材は、亜鉛およびアルミニウムがすべてマグネシウムに固溶していると考えられるため、微細な粒子が析出しにくいと推定される。 The same material as in Example 2 was used, the processing temperature was set to 300 ° C., and grooved rolling was repeated 15 times, and the total cross-section reduction rate was set to 92%. Produced. The obtained rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in Table 1. Compared with Comparative Example 5 in which the total cross-section reduction rate is the same, but compared with Comparative Example 5 in which fine particles do not exist, the magnesium alloy of Example 5 in which the quasicrystalline particles, which are fine particles, are dispersed inside the subcrystalline grains is An improvement in yield anisotropy is observed. In the commercial magnesium alloy extruded material of Comparative Example 5, since it is considered that zinc and aluminum are all dissolved in magnesium, it is estimated that fine particles are difficult to precipitate.
実施例３と同じ材料を使用し、加工温度が３００℃としたことと、溝ロール圧延を１５回繰り返し、総断面減少率を９２％にしたこと以外は実施例１と同様にして圧延材を作製した。図５は、ＳＥＭ/ＥＢＳＤによる微細組織の観察例である。図５図中の符号ＲＤが溝ロール圧延に平行な方向であり、符号ＴＤが溝ロール圧延に垂直な方向である。図５図中には、ＥＢＳＤによる結晶方位解析による、方位差角が１５度以上である大傾角粒界を黒色の曲線群で示している。図５図中に符号Ｇで示したのが、大傾角粒界で囲まれた結晶粒、すなわち、大傾角粒の一つであり、このような結晶粒の平均粒径は、１．７μmであった。結晶粒は、全体的に均一なサイズで分布していることが確認される。この圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を表１に示した。総断面減少率が同じであるが、微細な粒子が存在しない比較例５と比べると、微細な粒子である準結晶粒子が、亜結晶粒の内部に分散している実施例６のマグネシウム合金は、降伏異方性の改善が認められる。準結晶粒が亜結晶粒の内部に分散していることは、ＴＥＭ観察により確認した。 The same material as in Example 3 was used, the rolling temperature was set to 300 ° C., and groove rolling was repeated 15 times, and the rolled material was prepared in the same manner as in Example 1 except that the total cross-section reduction rate was 92%. Produced. FIG. 5 is an example of observation of a fine structure by SEM / EBSD. In FIG. 5, reference numeral RD is a direction parallel to the groove roll rolling, and reference numeral TD is a direction perpendicular to the groove roll rolling. In FIG. 5, a large tilt grain boundary having an orientation difference angle of 15 degrees or more by a crystal orientation analysis by EBSD is shown by a group of black curves. In FIG. 5, a symbol G indicates a crystal grain surrounded by a large tilt grain boundary, that is, one of the large tilt grains. The average grain size of such a crystal grain is 1.7 μm. there were. It is confirmed that the crystal grains are distributed with a uniform size as a whole. This rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in Table 1. Compared with Comparative Example 5 in which the total cross-section reduction rate is the same, but compared with Comparative Example 5 in which fine particles do not exist, the magnesium alloy of Example 6 in which the quasicrystalline particles, which are fine particles, are dispersed inside the subcrystalline grains is An improvement in yield anisotropy is observed. It was confirmed by TEM observation that the quasi-crystal grains were dispersed inside the sub-crystal grains.
実施例４と同じ材料を使用し、加工温度を２００℃としたことと、溝ロール圧延を１５回繰り返し、総断面減少率を９２％としたこと以外は実施例１と同様にして圧延材を作製した。この圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を表１に示した。総断面減少率が同じであるが、微細な粒子が存在しない比較例５と比べると、微細な粒子が、亜結晶粒の内部に分散している実施例７のマグネシウム合金は、６％高い引張強度を示すとともに、降伏異方性の改善が認められる。なお、微細な粒子は、マグネシウム母相と非整合界面を形成し、Ｍｇ２Ｚｎからなる第二相析出粒子である。The same material as in Example 4 was used, and the rolling material was processed in the same manner as in Example 1 except that the processing temperature was 200 ° C. and the groove roll rolling was repeated 15 times, and the total cross-section reduction rate was 92%. Produced. This rolled material was also subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in Table 1. Compared with Comparative Example 5 in which the total cross-sectional reduction rate is the same, but the fine particles are not present, the magnesium alloy of Example 7 in which fine particles are dispersed inside the sub-crystal grains is 6% higher in tensile strength. It shows strength and improved yield anisotropy. The fine particles are second-phase precipitated particles that form an inconsistent interface with the magnesium matrix and are composed of Mg 2 Zn.
商用マグネシウム合金押出材（ＡＺ６１：１質量％の亜鉛６と質量％のアルミニウムを添加）を使用し、機械加工により直径４０mmの圧延用ビレットを作製した。その後、加工温度を２００℃にしたことと、溝ロール圧延を１５回繰り返し、総断面減少率を９２％としたこと以外は、実施例１と同じ条件で圧延材を作製した。この圧延材について、実施例１と同じ条件で引張・圧縮試験を行った。得られた結果を表１に示した。降伏異方性比が１に近い値を示し、等方変形することが可能なマグネシウム合金が得られている。図８および図９は、それぞれ、実施例８のマグネシウム合金のＴＥＭ、ＳＥＭ/ＥＢＳＤによる微細組織の観察例である。図８において、符号Ｐで示した、約１００nm程度の微細な粒子の分散が確認される。この微細な粒子は、マグネシウム母相と非整合界面を形成し、Ｍｇ１７Ａｌ１２からなる第二相析出粒子である。また、図９において、符号Ｇで代表される、大傾角粒界で囲まれた結晶粒の平均粒径は、２．２μmであり、全体的に均一なサイズで分布していることが確認される。また、比較例５と比べると、実施例８に示したマグネシウム合金は、１５％高い引張強度および３０％以上高い圧縮強度を示し、微細な粒子の存在がより高強度化に寄与することが分かる。
[比較例１]A commercial magnesium alloy extruded material (AZ61: 1% by mass of zinc 6 and mass% of aluminum added) was used to produce a billet for rolling having a diameter of 40 mm by machining. Then, the rolling material was produced on the same conditions as Example 1 except having made processing temperature into 200 degreeC, repeating groove roll rolling 15 times, and making the total cross-section reduction rate 92%. This rolled material was subjected to a tension / compression test under the same conditions as in Example 1. The obtained results are shown in Table 1. A magnesium alloy having a yield anisotropy ratio close to 1 and capable of isotropic deformation is obtained. 8 and 9 are examples of observation of the microstructure of the magnesium alloy of Example 8 by TEM and SEM / EBSD, respectively. In FIG. 8, the dispersion of fine particles of about 100 nm indicated by the symbol P is confirmed. These fine particles are second-phase precipitated particles that form an inconsistent interface with the magnesium matrix and are composed of Mg 17 Al 12 . In addition, in FIG. 9, the average grain size of the crystal grains surrounded by the large-angle boundaries represented by the symbol G is 2.2 μm, and it is confirmed that they are distributed in a uniform size as a whole. The In addition, compared with Comparative Example 5, the magnesium alloy shown in Example 8 shows 15% higher tensile strength and 30% or higher compressive strength, and it can be seen that the presence of fine particles contributes to higher strength. .
[Comparative Example 1]
商用純マグネシウム（純度９９．９５％）に７．５質量％の亜鉛と１．７質量％イットリウムを溶解し、鋳造して母合金を作製した。この母合金を溶体化処理した後、機械加工により直径４０mmの押出ビレットを作製した。この押出ビレットを約２３０℃に昇温した押出コンテナに投入し、３０分程度保持した後、断面減少率が９４％となる押出比２５：１で温間押出加工を行い、直径８mmの押出材を得た。この押出材について、実施例１と同じ条件にて引張試験を行った。その結果を図２と表１に示した。
[比較例２]7.5 mass% zinc and 1.7 mass% yttrium were dissolved in commercial pure magnesium (purity 99.95%) and cast to prepare a master alloy. After this mother alloy was subjected to solution treatment, an extruded billet having a diameter of 40 mm was produced by machining. This extruded billet is put into an extrusion container heated to about 230 ° C., held for about 30 minutes, and then subjected to warm extrusion at an extrusion ratio of 25: 1 with a cross-section reduction rate of 94%, and an extruded material having a diameter of 8 mm. Got. The extruded material was subjected to a tensile test under the same conditions as in Example 1. The results are shown in FIG.
[Comparative Example 2]
商用純マグネシウム（純度９９．９５％）に８質量％の亜鉛と４質量％のアルミニウムを溶解し、鋳造して母合金を作製した。その後の加工は比較例１と同じとした。得られた押出材について、実施例１と同し条件で引張試験を行った。その結果を図２と表１に示した。
[比較例３]8 mass% zinc and 4 mass% aluminum were melt | dissolved in commercial pure magnesium (purity 99.95%), and the mother alloy was produced by casting. Subsequent processing was the same as in Comparative Example 1. The obtained extruded material was subjected to a tensile test under the same conditions as in Example 1. The results are shown in FIG.
[Comparative Example 3]
商用純マグネシウム（純度９９．９５％）に６質量％の亜鉛と３質量％のアルミニウムを溶解し、鋳造して母合金を作製した。その後の加工は比較例１と同じとした。得られた押出材について、実施例１と同し条件で引張試験を行った。その結果を図２と表１に示した。
[比較例４]6 mass% zinc and 3 mass% aluminum were melt | dissolved in commercial pure magnesium (purity 99.95%), and the mother alloy was produced by casting. Subsequent processing was the same as in Comparative Example 1. The obtained extruded material was subjected to a tensile test under the same conditions as in Example 1. The results are shown in FIG.
[Comparative Example 4]
商用マグネシウム合金押出材（ＡＺ３１：１質量％の亜鉛と３質量％のアルミニウムを添加）を使用し、機械加工により直径４０mmの圧延用ビレットを作製した。その後、加工温度を２００℃にしたこと以外は実施例１と同様にして圧延材を作製した。図６は、この圧延材のＴＥＭによる微細組織の観察例である。実施例１のマグネシウム合金と同様に、亜結晶粒から微細組織が形成されているが、亜結晶粒の内部に微細な粒子は存在していない。比較例４の圧延材についても、実施例１と同じ条件で引張・圧縮試験を行った。その結果を表１に示した。
[比較例５]A commercial magnesium alloy extruded material (AZ31: 1% by mass of zinc and 3% by mass of aluminum added) was used to produce a billet for rolling having a diameter of 40 mm by machining. Thereafter, a rolled material was produced in the same manner as in Example 1 except that the processing temperature was 200 ° C. FIG. 6 is an example of observation of the microstructure of the rolled material by TEM. Similar to the magnesium alloy of Example 1, a fine structure is formed from subcrystalline grains, but no fine grains are present inside the subcrystalline grains. The rolled material of Comparative Example 4 was also subjected to a tension / compression test under the same conditions as in Example 1. The results are shown in Table 1.
[Comparative Example 5]
比較例４と同じ材料を使用し、加工温度を２００℃としたこと、溝ロール圧延を１５回繰り返し、総断面減少率を９２％としたこと以外は実施例１と同じ条件で圧延材を作製した。この圧延材についても、実施例１と同し条件で引張・圧縮試験を行った。その結果を表１に示した。 The same material as in Comparative Example 4 was used, and the rolled material was produced under the same conditions as in Example 1 except that the processing temperature was 200 ° C., the groove roll rolling was repeated 15 times, and the total cross-section reduction rate was 92%. did. This rolled material was also subjected to a tensile / compression test under the same conditions as in Example 1. The results are shown in Table 1.
本発明のマグネシウム合金は、強度および延性の向上が図られ、より実用的なマグネシウム合金であり、工業用材料としての使用が見込まれる。 The magnesium alloy of the present invention is improved in strength and ductility, is a more practical magnesium alloy, and is expected to be used as an industrial material.
Claims (4)
６≦Ａ＜１０のとき、Ｚは、Ａｌ、Ｚｒ、Ｃａ、Ｓｎ、Ｌｉ、Ａｇまたは希土類元素のうちのいずれか一種であり、０＜Ｂ＜１０であり、
０＜Ａ＜６のとき、Ｚは、Ａｌであり、６≦Ｂ＜１０であり、
溝ロール圧延により断面減少率が９０％以上である加工ひずみが導入され、方位差角が１５度以上の粒界である大傾角粒界を有し、この大傾角粒界に囲まれた結晶粒の内部が亜結晶粒から形成され、前記亜結晶粒の内部に、平均粒径が１０nm以上１μm以下の微細な粒子が分散していることを特徴とするマグネシウム合金。 A chemical composition represented by Mg-Amass% Zn-Bmass% Z (Mg: magnesium, Zn: zinc, Z: other metal elements), and a magnesium alloy containing inevitable impurities,
When 6 ≦ A <10, Z is any one of Al, Zr, Ca, Sn, Li, Ag, or a rare earth element, and 0 <B <10.
When 0 <A <6, Z is Al, 6 ≦ B <10,
A processing strain having a cross-sectional reduction rate of 90% or more is introduced by groove roll rolling , and there is a large tilt grain boundary that is a grain boundary having an orientation difference angle of 15 degrees or more, and the crystal grains surrounded by the large tilt grain boundary The magnesium alloy is formed of subcrystalline grains, and fine grains having an average grain size of 10 nm or more and 1 μm or less are dispersed inside the subcrystalline grains .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012505620A JP5557121B2 (en) | 2010-03-17 | 2011-03-07 | Magnesium alloy |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010060144 | 2010-03-17 | ||
| JP2010060144 | 2010-03-17 | ||
| PCT/JP2011/055271 WO2011114931A1 (en) | 2010-03-17 | 2011-03-07 | Magnesium alloy |
| JP2012505620A JP5557121B2 (en) | 2010-03-17 | 2011-03-07 | Magnesium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2011114931A1 JPWO2011114931A1 (en) | 2013-06-27 |
| JP5557121B2 true JP5557121B2 (en) | 2014-07-23 |
Family
ID=44649029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012505620A Expired - Fee Related JP5557121B2 (en) | 2010-03-17 | 2011-03-07 | Magnesium alloy |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20130039805A1 (en) |
| JP (1) | JP5557121B2 (en) |
| KR (1) | KR101405079B1 (en) |
| CN (1) | CN102933730B (en) |
| WO (1) | WO2011114931A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2797499T3 (en) | 2012-06-26 | 2020-12-02 | Biotronik Ag | This patent application refers to an implant made of a magnesium alloy and to a method for the production thereof. |
| WO2014001240A1 (en) | 2012-06-26 | 2014-01-03 | Biotronik Ag | Magnesium-aluminum-zinc alloy, method for the production thereof and use thereof |
| SG11201406024QA (en) | 2012-06-26 | 2014-10-30 | Biotronik Ag | Magnesium alloy, method for the production thereof and use thereof |
| SG11201406026TA (en) | 2012-06-26 | 2014-10-30 | Biotronik Ag | Magnesium-zinc-calcium alloy, method for production thereof, and use thereof |
| JP6373557B2 (en) * | 2013-02-08 | 2018-08-15 | 国立研究開発法人物質・材料研究機構 | Magnesium wrought alloy and method for producing the same |
| JP6392250B2 (en) * | 2013-02-15 | 2018-09-19 | ボストン サイエンティフィック サイムド，インコーポレイテッドＢｏｓｔｏｎ Ｓｃｉｅｎｔｉｆｉｃ Ｓｃｉｍｅｄ，Ｉｎｃ． | Biodegradable endoprosthesis and method of processing biodegradable magnesium alloy used therein |
| CA2929046A1 (en) * | 2013-10-29 | 2015-05-07 | Boston Scientific Scimed, Inc. | Bioerodible magnesium alloy microstructures for endoprostheses |
| US11198926B2 (en) * | 2013-12-17 | 2021-12-14 | Northwestern University | Alloys and methods of forming same |
| TWI504754B (en) * | 2014-03-28 | 2015-10-21 | Nippon Steel & Sumitomo Metal Corp | Plated steel sheet with quasicrystal |
| KR101823286B1 (en) | 2014-03-28 | 2018-01-29 | 신닛테츠스미킨 카부시키카이샤 | Plated steel sheet containing quasicrystal |
| CN107427603A (en) | 2015-03-11 | 2017-12-01 | 波士顿科学国际有限公司 | Bioerodible magnesium alloy micro-structural for interior prosthese |
| WO2018083998A1 (en) * | 2016-11-02 | 2018-05-11 | 国立大学法人 熊本大学 | Bioabsorbable medical device and method for producing same |
| JP6860235B2 (en) * | 2017-07-10 | 2021-04-14 | 国立研究開発法人物質・材料研究機構 | Magnesium-based alloy wrought material and its manufacturing method |
| US11578396B2 (en) * | 2017-07-18 | 2023-02-14 | National Institute For Materials Science | Magnesium-based alloy wrought product and method for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000271693A (en) * | 1999-03-26 | 2000-10-03 | Ykk Corp | Production of magnesium alloy material |
| JP2000313948A (en) * | 1999-04-27 | 2000-11-14 | Ykk Corp | Manufacture of forming material and formed article |
| JP2005029871A (en) * | 2003-07-11 | 2005-02-03 | Matsushita Electric Ind Co Ltd | Magnesium alloy sheet material and manufacturing method therefor |
| JP2007291488A (en) * | 2006-03-30 | 2007-11-08 | Univ Of Electro-Communications | Method and device for producing magnesium alloy material, and magnesium alloy material |
| WO2009044829A1 (en) * | 2007-10-02 | 2009-04-09 | National Institute For Materials Science | Magnesium alloy |
-
2011
- 2011-03-07 WO PCT/JP2011/055271 patent/WO2011114931A1/en active Application Filing
- 2011-03-07 US US13/635,491 patent/US20130039805A1/en not_active Abandoned
- 2011-03-07 JP JP2012505620A patent/JP5557121B2/en not_active Expired - Fee Related
- 2011-03-07 KR KR1020127024201A patent/KR101405079B1/en not_active IP Right Cessation
- 2011-03-07 CN CN201180014451.5A patent/CN102933730B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000271693A (en) * | 1999-03-26 | 2000-10-03 | Ykk Corp | Production of magnesium alloy material |
| JP2000313948A (en) * | 1999-04-27 | 2000-11-14 | Ykk Corp | Manufacture of forming material and formed article |
| JP2005029871A (en) * | 2003-07-11 | 2005-02-03 | Matsushita Electric Ind Co Ltd | Magnesium alloy sheet material and manufacturing method therefor |
| JP2007291488A (en) * | 2006-03-30 | 2007-11-08 | Univ Of Electro-Communications | Method and device for producing magnesium alloy material, and magnesium alloy material |
| WO2009044829A1 (en) * | 2007-10-02 | 2009-04-09 | National Institute For Materials Science | Magnesium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101405079B1 (en) | 2014-06-10 |
| US20130039805A1 (en) | 2013-02-14 |
| JPWO2011114931A1 (en) | 2013-06-27 |
| KR20120121405A (en) | 2012-11-05 |
| CN102933730B (en) | 2015-12-02 |
| CN102933730A (en) | 2013-02-13 |
| WO2011114931A1 (en) | 2011-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5557121B2 (en) | Magnesium alloy | |
| Homma et al. | Fabrication of extraordinary high-strength magnesium alloy by hot extrusion | |
| Ding et al. | Texture weakening and ductility variation of Mg–2Zn alloy with CA or RE addition | |
| Xu et al. | Extruded Mg–Zn–Ca–Mn alloys with low yield anisotropy | |
| JP4189687B2 (en) | Magnesium alloy material | |
| JP5252583B2 (en) | Mg alloy and manufacturing method thereof | |
| JP5540415B2 (en) | Mg-based alloy | |
| CN105154734B (en) | It is a kind of can high-speed extrusion wrought magnesium alloy and preparation method thereof | |
| Homma et al. | Room and elevated temperature mechanical properties in the as-extruded Mg–Al–Ca–Mn alloys | |
| JP5586027B2 (en) | Mg-based alloy | |
| JP6860235B2 (en) | Magnesium-based alloy wrought material and its manufacturing method | |
| KR101785121B1 (en) | Magnesium alloy sheet | |
| JP6860236B2 (en) | Magnesium-based alloy wrought material and its manufacturing method | |
| Braszczyńska-Malik | Spherical shape of γ-Mg17Al12 precipitates in AZ91 magnesium alloy processed by equal-channel angular pressing | |
| JP4803357B2 (en) | Heat-resistant magnesium alloy produced by hot working and method for producing the same | |
| KR101700419B1 (en) | Method for preparing high-strength magnesium alloy extruded material using low temperature and slow speed extrusion process and magnesium alloy extruded material manufactured thereby | |
| JP6080067B2 (en) | Magnesium alloy | |
| CN112301261B (en) | Preparation method of ultrafine crystal or nanocrystalline magnesium-zinc alloy | |
| JP5403508B2 (en) | Mg alloy member. | |
| JP6035645B2 (en) | Method for producing magnesium alloy material | |
| WO2021215241A1 (en) | Magnesium alloy, magnesium alloy plate, magnesium alloy rod, methods for producing these, and magnesium alloy member | |
| JP2009084685A (en) | Warm working method of magnesium alloy, magnesium alloy for warm working and method for manufacturing the same | |
| JP4253846B2 (en) | Magnesium alloy wire, method for producing the same, and magnesium alloy molded body | |
| Wu et al. | Microstructure and mechanical properties of ARB processed Mg-3% Gd alloy | |
| JP5561592B2 (en) | Magnesium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140212 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140304 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140430 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140522 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5557121 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |