JP2010013725A - Easily formable magnesium alloy sheet and method for production thereof - Google Patents
Easily formable magnesium alloy sheet and method for production thereof Download PDFInfo
- Publication number
- JP2010013725A JP2010013725A JP2008292848A JP2008292848A JP2010013725A JP 2010013725 A JP2010013725 A JP 2010013725A JP 2008292848 A JP2008292848 A JP 2008292848A JP 2008292848 A JP2008292848 A JP 2008292848A JP 2010013725 A JP2010013725 A JP 2010013725A
- Authority
- JP
- Japan
- Prior art keywords
- magnesium alloy
- mass
- alloy sheet
- total amount
- rare earth
- 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.)
- Granted
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 182
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 69
- 238000005096 rolling process Methods 0.000 claims abstract description 61
- 238000000137 annealing Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 22
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 22
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 22
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 21
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 83
- 239000000956 alloy Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 13
- 238000001028 reflection method Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 11
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 7
- 238000005098 hot rolling Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- 239000011701 zinc Substances 0.000 description 55
- 238000012360 testing method Methods 0.000 description 49
- 239000011777 magnesium Substances 0.000 description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 28
- 229910052749 magnesium Inorganic materials 0.000 description 28
- 229910000838 Al alloy Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 10
- 229910000882 Ca alloy Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910003120 Zn-Ce Inorganic materials 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 229910000636 Ce alloy Inorganic materials 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 229910007612 Zn—La Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004899 motility Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000858 La alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019400 Mg—Li Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910009378 Zn Ca Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 and if necessary Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- 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
- C22C23/06—Alloys based on magnesium with a rare earth metal 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
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)
- Heat Treatment Of Sheet Steel (AREA)
- Forging (AREA)
- Metal Rolling (AREA)
Abstract
Description
本発明は、易成形性マグネシウム合金の製造方法、そのマグネシウム合金板材、マグネシウム合金製プレス成形体及びマグネシウム合金製部材に関するものであり、更に詳しくは、軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）、及びＺｎを含み、Ｍｎ、Ｚｒを特定量添加したマグネシウム合金を、熱間・温間圧延し、焼鈍を行うことで、集合組織を改質し、常温においても、５０００系もしくは６０００系アルミニウム合金並の成形性を有することを可能とする易成形性マグネシウム合金板材の製造方法、マグネシウム合金板材、そのプレス成形体及び部材に関するものである。 The present invention relates to a method for producing an easily moldable magnesium alloy, its magnesium alloy sheet, a magnesium alloy press-molded body, and a magnesium alloy member, and more particularly, a light rare earth element (Y, Sc, La, Ce, A magnesium alloy containing a specific amount of Mn and Zr containing Pr, Nd, Sm) and Zn is hot / warm-rolled and annealed to modify the texture, even at room temperature, 5000 The present invention relates to a method for producing an easily formable magnesium alloy plate material that can have formability equivalent to that of a 6000 series aluminum alloy, a magnesium alloy plate material, a press-formed body thereof, and a member.
更に、本発明は、上記軽希土類元素の代わるＣａ、及びＺｎを含み、Ａｌ、Ｍｎ、Ｚｒを特定量添加したマグネシウム合金を、熱間・温間圧延し、焼鈍を行うことで、集合組織を改質し、常温においても、５０００系もしくは６０００系アルミニウム合金並の成形性を有することを可能とする易成形性マグネシウム合金板材の製造方法、マグネシウム合金板材、そのプレス成形体及び部材に関するものである。本発明は、宇宙・航空材料、電子機器材料、自動車部材等の幅広い分野で利用することが可能な易成形性マグネシウム合金板材、そのプレス成形体及び筐体等のマグネシウム合金製部材を提供するものである。 Furthermore, the present invention includes a magnesium alloy containing Ca and Zn in place of the light rare earth elements and added with a specific amount of Al, Mn, and Zr, hot and warm rolled, and annealed to obtain a texture. The present invention relates to a method for producing an easily formable magnesium alloy plate material that can be reformed and has formability comparable to that of a 5000-series or 6000-series aluminum alloy even at room temperature, a magnesium alloy sheet, a press-molded body thereof, and a member. . The present invention provides an easily formable magnesium alloy plate material that can be used in a wide range of fields such as space / aviation materials, electronic equipment materials, automobile members, etc., and press-formed bodies and magnesium alloy members such as housings. It is.
マグネシウムは、実用構造金属材料中、最も低密度（＝１．７ｇ／ｃｍ３）であり、金属材料特有の易リサイクル性を有し、資源も豊富に存在することから、次世代の構造用軽量材料として注目されている。現在、日本におけるマグネシウム製品の多くは、ダイキャスト等の鋳造法により作製されている。これらの手法により、薄肉成形が可能となったことが、マグネシウム合金の工業化を助長した最大の要因である。 Magnesium has the lowest density (= 1.7 g / cm 3 ) among practical structural metal materials, has easy recyclability unique to metal materials, and has abundant resources. It is attracting attention as a material. Currently, many magnesium products in Japan are produced by die casting or other casting methods. The fact that thin molding is possible by these methods is the biggest factor that promoted the industrialization of magnesium alloys.
特に、家電製品では、パソコン、携帯電話、デジタルカメラ等の家電製品筐体に、マグネシウム合金鋳造材が利用されている。しかし、現状の鋳造法による生産法には、鋳造欠陥を補うための後処理が必要であること、歩留りが低いこと、部材の強度・剛性に問題があること、等の問題が存在する。 In particular, in household electrical appliances, magnesium alloy castings are used in household electrical appliance casings such as personal computers, mobile phones, and digital cameras. However, the current production methods using casting methods have problems such as the need for post-processing to compensate for casting defects, low yields, and problems with the strength and rigidity of members.
一般的に、プレス成形は、歩留まりが高く、成形と同時に高強度・高靭性化を図ることができることから、需要拡大の有効な手段と言える。マグネシウム合金製板材から、プレス成形により成形体を作製できる場合、薄肉、かつ高強度な成形体を、安価なプロセスで、作製することができ、家電製品筐体等の分野で、多くの需要が予測できる。 In general, press molding can be said to be an effective means of increasing demand because it has a high yield and can achieve high strength and toughness simultaneously with molding. When a compact can be produced from a magnesium alloy sheet by press molding, a thin and high-strength compact can be produced by an inexpensive process, and there is a great demand in the field of household appliances and other products. Predictable.
金属の塑性変形の基本となる転位の運動性は、すべり面間隔／原子間距離の比に影響されることが知られている。したがって、最密六方構造（ＨＣＰ構造）であるマグネシウム合金の場合、ａ軸長さとｃ軸長さの比（ｃ／ａ比）が大きく（ｃ／ａ＝１．６２３６）、底面すべりと非底面すべりでは、転位の運動性に大きな違いが生じる。 It is known that dislocation motility, which is the basis of plastic deformation of metals, is affected by the ratio of slip plane spacing / interatomic distance. Therefore, in the case of a magnesium alloy having a close-packed hexagonal structure (HCP structure), the ratio of the a-axis length to the c-axis length (c / a ratio) is large (c / a = 1.6236), and bottom slip and non-bottom surface Slip makes a big difference in dislocation motility.
そのため、マグネシウム合金の非底面すべりの臨界分解せん断応力（ＣＲＳＳ）は、常温において、他のすべり系と比較して、非常に大きく、常温成形性は、必然的に低い。更に、マグネシウム合金板材には、（０００２）面が、板面に対して、平行に配向する集合組織が形成されるため、塑性変形時の板厚方向の歪みが期待できず、そのことが、常温成形性を妨げる一因となっている。 Therefore, the critical decomposition shear stress (CRSS) of the non-bottom slip of the magnesium alloy is very large at room temperature as compared with other slip systems, and the room temperature formability is inevitably low. Furthermore, since a texture is formed in the magnesium alloy plate material in which the (0002) plane is oriented parallel to the plate surface, distortion in the plate thickness direction during plastic deformation cannot be expected. This is one factor that hinders room temperature moldability.
成形性に乏しいマグネシウム合金の、常温成形性を向上させる手法としては、規定量のリチウムを添加したマグネシウム合金板材を利用する手法が知られている（特許文献１，２）。この方法は、具体的には、マグネシウム（合金）に、８質量％以上のＬｉを添加し、ＨＣＰ構造を有するマグネシウム中に、体心立方晶（β相）を晶出させ、成形性を著しく向上させるものである。更に、Ｌｉの添加により、ｃ／ａ比を低め（非特許文献１）、相乗的に成形性を向上させるものである。一方、Ｌｉの添加は、マグネシウムの腐食特性を著しく劣化させるため、実用的ではない。それゆえに、Ｌｉを添加せずに、成形性を向上させる技術が望まれている。 As a technique for improving the room temperature formability of a magnesium alloy having poor formability, a technique using a magnesium alloy sheet material to which a specified amount of lithium is added is known (Patent Documents 1 and 2). Specifically, in this method, 8% by mass or more of Li is added to magnesium (alloy), and body-centered cubic (β phase) is crystallized in magnesium having an HCP structure, so that formability is remarkably improved. It is to improve. Furthermore, the addition of Li lowers the c / a ratio (Non-Patent Document 1) and synergistically improves the moldability. On the other hand, the addition of Li is not practical because it significantly deteriorates the corrosion characteristics of magnesium. Therefore, a technique for improving moldability without adding Li is desired.
Ｌｉを添加せずに、マグネシウム合金の常温成形性を改善する手段としては、異周速圧延（非特許文献２参照）、クロス圧延法（特許文献３参照）を利用して、（０００２）面の集合組織形成を弱めた圧延材を作製する方法が挙げられる。本手法を利用すると、油性潤滑剤が十分利用可能な、１５０〜２３０℃の温度でも、高い成形性（エリクセン値：約１３）を確保することができる。しかし、本手法により作製されたマグネシウム合金の、常温（３０℃）における成形性は、低いものであり、せいぜい、エリクセン値で、６程度である（非特許文献３参照）。 As means for improving the room temperature formability of the magnesium alloy without adding Li, the (0002) plane is utilized by utilizing different peripheral speed rolling (see non-patent document 2) and cross rolling method (see patent document 3). There is a method of producing a rolled material in which the texture formation is weakened. When this method is used, high moldability (Erichsen value: about 13) can be secured even at a temperature of 150 to 230 ° C. at which an oil-based lubricant can be sufficiently used. However, the formability of the magnesium alloy produced by this method at room temperature (30 ° C.) is low, and at most, the Erichsen value is about 6 (see Non-Patent Document 3).
更に、低温（１５０℃以下）で、プレス成形を実現する手段としては、適当な熱処理を経た、Ｃｅ、Ｌａ、Ｙ等の軽希土類元素を、適当量添加したマグネシウム合金板材を利用することが挙げられる（特許文献４参照）。この手法は、軽希土類元素を、適当量添加して、マグネシウムのｃ／ａ比を低め、マグネシウムの塑性異方性を軽減するものである。しかし、この手法により作製されたマグネシウム合金の、常温（３０℃）における成形性は、エリクセン値で、せいぜい４〜５程度である。 Furthermore, as a means for realizing press molding at a low temperature (150 ° C. or less), it is possible to use a magnesium alloy plate material to which an appropriate amount of light rare earth elements such as Ce, La, Y, etc., which has been subjected to an appropriate heat treatment, is added. (See Patent Document 4). In this method, an appropriate amount of a light rare earth element is added to lower the c / a ratio of magnesium and reduce the plastic anisotropy of magnesium. However, the formability of the magnesium alloy produced by this method at room temperature (30 ° C.) is an Erichsen value of about 4 to 5 at most.
現在、幅広い分野で利用されているアルミニウム合金の常温成形性（エリクセン値）は、上記のマグネシウム合金よりも著しく高く、５０００系合金では、８．３（５０８３−Ｏ材）、６０００系合金では、９．２（６０６１−Ｔ４材）、１０００系合金では、１１．０（１１００−Ｏ材）である（非参考文献４参照）。 Currently, the room temperature formability (Ericsen value) of aluminum alloys used in a wide range of fields is significantly higher than the above magnesium alloys, 8.3 (5083-O material) for 5000 series alloys, and 6000 series alloys, In the case of 9.2 (6061-T4 material) and 1000 series alloys, it is 11.0 (1100-O material) (see non-reference document 4).
したがって、マグネシウム合金に関しても、今後、マグネシウム合金板材の著しい需要増加を見込むためには、アルミニウム合金板材に準ずる、もしくは匹敵する常温成形性（常温でのエリクセン値が８．０以上）を付与することが必要であり、当技術分野においては、優れた易成形性を有する新しいマグネシウム合金板材の製造技術及びその製品を開発することが強く要請されていた。 Therefore, regarding the magnesium alloy, in order to expect a significant increase in demand for the magnesium alloy sheet in the future, the room temperature formability equivalent to or comparable to that of the aluminum alloy sheet (Ericsen value at room temperature of 8.0 or higher) should be imparted. In this technical field, there has been a strong demand for the development of new magnesium alloy sheet manufacturing technology and products having excellent easy formability.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、アルミニウム合金板材に準ずる、もしくは匹敵する常温成形性、すなわち、常温でのエリクセン値が８．０以上の成形性を有する優れた易成形性マグネシウム合金板材を製造することを目標として鋭意研究を重ねた結果、マグネシウムに、特定量の軽希土類元素類（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、Ｚｎ、及び必要により、Ｍｎ、Ｚｒを添加した合金を、適当な条件で熱間・温間圧延し、更に、適当な熱処理に供することにより、集合組織を改質し、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する、優れた易成形性を有するマグネシウム合金板材を作製することに成功した。 Under such circumstances, in view of the above prior art, the present inventors have a room temperature formability equivalent to or comparable to an aluminum alloy sheet, that is, a formability having an Erichsen value of 8.0 or more at room temperature. As a result of earnest research for the purpose of producing an excellent easily-formable magnesium alloy sheet having 1 as a result of magnesium, 1 of a specific amount of light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm) An alloy added with seeds or more, Zn, and if necessary, Mn and Zr is hot / warm-rolled under appropriate conditions, and further subjected to an appropriate heat treatment to modify the texture, so that the room temperature (30 C.) and succeeded in producing a magnesium alloy sheet having excellent easy formability, which is equivalent to or comparable to an aluminum alloy.
また、マグネシウムに、特定量のＣａ、Ｚｎ、及び必要により、Ａｌ、Ｍｎ、Ｚｒを添加した合金を、適当な条件で熱間・温間圧延し、更に、適当な熱処理に供することにより、集合組織を改質し、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する、優れた易成形性を有するマグネシウム合金板材を作製することに成功し、本発明を完成するに至った。 In addition, an alloy obtained by adding a specific amount of Ca, Zn, and, if necessary, Al, Mn, Zr to magnesium, is subjected to hot / warm rolling under appropriate conditions, and further subjected to appropriate heat treatment to form an aggregate. The present inventors have succeeded in producing a magnesium alloy sheet material having excellent easy formability, which is similar to or comparable to an aluminum alloy at room temperature (30 ° C.), and has completed the present invention.
本発明は、優れた成形性を有する易成形性マグネシウム合金板材の製造方法を提供することを目的とするものである。また、本発明は、該マグネシウム合金板材を成形して、複雑形状を有するマグネシウム合金製プレス成形体及びマグネシウム合金製部材を常温で作製する当該マグネシウム合金製プレス成形体等の製造方法を提供することを目的とするものである。更に、本発明は、上記手法により作製されたマグネシウム合金板材、マグネシウム合金製プレス成形体及びマグネシウム合金製部材を提供することを目的とするものである。 An object of this invention is to provide the manufacturing method of the easily moldable magnesium alloy board | plate material which has the outstanding moldability. The present invention also provides a method for producing a magnesium alloy press-molded body having a complex shape and a magnesium alloy press-formed body that is produced at room temperature by forming the magnesium alloy sheet material at a normal temperature. It is intended. Furthermore, this invention aims at providing the magnesium alloy board | plate material produced by the said method, the magnesium alloy press-molded body, and the magnesium alloy member.
（１）軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、及びＺｎを含み、軽希土類元素の総量が０．０１〜１．０質量％であり、Ｚｎの総量が０．４〜２．６質量％であり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金を、熱間・温間圧延し、圧延後に焼鈍を行うことにより、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有するマグネシウム合金板材を製造することを特徴とする易成形性マグネシウム合金板材の製造方法。
（２）Ｙ及び／又はＳｃの総量が、０．５質量％以下である、前記（１）に記載の易成形性マグネシウム合金板材の製造方法。
（３）軽希土類元素の総量が、０．０１〜０．７質量％である、前記（１）又は（２）に記載の易成形性マグネシウム合金板材の製造方法。
（４）軽希土類元素として、軽希土類元素を主成分とする希土類元素混合物（ミッシュメタル：Ｍｍ）を使用する、前記（１）〜（３）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（５）軽希土類元素に代わるＣａ、及びＺｎを含み、Ｃａの総量が０．０１〜０．６質量％であり、Ｚｎの総量が０．４〜２．６質量％であり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金を、熱間・温間圧延し、圧延後に焼鈍を行うことにより、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有するマグネシウム合金板材を製造することを特徴とする易成形性マグネシウム合金板材の製造方法。
（６）Ｃａの総量が、０．０１〜０．３質量％である、前記（５）に記載の易成形性マグネシウム合金板材の製造方法。
（７）更に、総量が０．０１〜２．０質量％であるＡｌを添加する、前記（５）又は（６）に記載の易成形性マグネシウム合金板材の製造方法。
（８）更に、総量が０．０１〜０．８質量％であるＭｎ及び／又はＺｒを添加する、前記（１）から（７）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（９）Ｍｎ及び／又はＺｒの総量が、０．０１〜０．５質量％である、前記（８）に記載の易成形性マグネシウム合金板材の製造方法。
（１０）試料温度を４００℃〜５００℃で熱間圧延する、前記（１）〜記（９）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（１１）総圧下率３０％以上の熱間・温間圧延を行う、前記（１）〜（１０）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（１２）熱間・温間圧延した後に、熱処理による焼鈍を行う、前記（１）から（１１）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（１３）熱処理による焼鈍により、粒界の新しい配列を伴う再結晶を起こす、前記（１２）に記載の易成形性マグネシウム合金板材の製造方法。
（１４）焼鈍時の試料温度が、２６０℃〜４５０℃、保持時間が、１０分〜３時間である、前記（１２）又は（１３）に記載の易成形性マグネシウム合金板材の製造方法。
（１５）焼鈍時の試料温度が、３００℃〜４００℃、保持時間が１０分〜３時間である、前記（１２）〜（１４）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（１６）Ｌｉの含有量が０．１質量％未満であり、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有することを特徴とする易成形性マグネシウム合金板材。
（１７）軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、及びＺｎを含み、軽希土類元素の総量が０．０１〜１．０質量％であり、Ｚｎの総量が０．４〜２．６質量％であり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金からなり、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有することを特徴とする易成形性マグネシウム合金板材。
（１８）Ｙ及び／又はＳｃの総量が、０．５質量％以下である、前記（１７）に記載の易成形性マグネシウム合金板材の製造方法。
（１９）軽希土類元素の総量が、０．０１〜０．７質量％である、前記（１７）〜（１８）のいずれかに記載の易成形性マグネシウム合金板材。
（２０）軽希土類元素として、軽希土類元素を主成分とする希土類元素混合物（ミッシュメタル：Ｍｍ）を使用したことを特徴とする、前記（１７）〜（１９）のいずれかに記載の易成形性マグネシウム合金板材。
（２１）軽希土類元素に代わるＣａ、及びＺｎを含み、Ｃａの総量が０．０１〜０．６質量％であり、Ｚｎの総量が、０．４〜２．６質量％であり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金をからなり、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有することを特徴とする易成形性マグネシウム合金板材。
（２２）Ｃａの総量が、０．０１〜０．３質量％である、前記（２１）記載の易成形性マグネシウム合金板材。
（２３）更に、総量が０．０１〜２．０質量％であるＡｌが添加されている、前記（２１）又は（２２）に記載の易成形性マグネシウム合金板材。
（２４）更に、総量が０．０１〜０．８質量％であるＭｎ及び／又はＺｒが添加されている、前記（１７）から（２３）のいずれかに記載の易成形性マグネシウム合金板材の製造方法。
（２５）Ｍｎ及び／又はＺｒの総量が、０．０１〜０．５質量％である、前記（２４）に記載の易成形性マグネシウム合金板材の製造方法。
（２６）常温（３０℃）で、エリクセン値が少なくとも８．０以上である、前記（１６）〜（２５）のいずれかに記載の易成形性マグネシウム合金板材。
（２７）前記（１６）〜（２６）のいずれかに記載の易成形性マグネシウム合金板材の成形体からなることを特徴とするマグネシウム合金製プレス成形体。
（２８）板幅方向に（０００２）面の極を有する集合組織を示す、前記（２７）に記載のマグネシウム合金製プレス成形体。
（２９）前記（２７）又は（２８）に記載のマグネシウム合金製プレス成形体からなることを特徴とするマグネシウム合金製部材。
(1) one or more light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm) and Zn, and the total amount of light rare earth elements is 0.01 to 1.0% by mass; XRD is obtained by hot-warming a magnesium alloy composed of 0.4 to 2.6% by mass and containing impurities inevitably mixed, and annealing after rolling. A magnesium alloy sheet material having a pole in the sheet width direction of the (0002) plane texture by measurement by a method (Schulz reflection method).
(2) The method for producing an easily formable magnesium alloy sheet according to (1), wherein the total amount of Y and / or Sc is 0.5% by mass or less.
(3) The method for producing an easily formable magnesium alloy sheet according to (1) or (2), wherein the total amount of light rare earth elements is 0.01 to 0.7% by mass.
(4) The easily formable magnesium alloy sheet according to any one of (1) to (3), wherein a rare earth element mixture (Misch metal: Mm) containing light rare earth elements as a main component is used as the light rare earth element. Production method.
(5) Including Ca and Zn instead of light rare earth elements, the total amount of Ca is 0.01 to 0.6% by mass, the total amount of Zn is 0.4 to 2.6% by mass, and other unavoidable A magnesium alloy constituted by containing impurities mixed in is hot-warm-rolled and annealed after rolling. As a result of measurement by the XRD method (Schulz reflection method), the (0002) plane texture A method for producing a readily formable magnesium alloy sheet, comprising producing a magnesium alloy sheet having poles in the sheet width direction.
(6) The method for producing an easily formable magnesium alloy sheet according to (5), wherein the total amount of Ca is 0.01 to 0.3% by mass.
(7) The method for producing an easily formable magnesium alloy sheet according to (5) or (6), further comprising adding Al having a total amount of 0.01 to 2.0% by mass.
(8) The method for producing an easily formable magnesium alloy sheet according to any one of (1) to (7), further comprising adding Mn and / or Zr having a total amount of 0.01 to 0.8% by mass. .
(9) The method for producing an easily formable magnesium alloy sheet according to (8), wherein the total amount of Mn and / or Zr is 0.01 to 0.5% by mass.
(10) The method for producing an easily formable magnesium alloy sheet according to any one of (1) to (9), wherein the sample is hot-rolled at a temperature of 400 ° C to 500 ° C.
(11) The method for producing an easily formable magnesium alloy sheet according to any one of (1) to (10), wherein hot / warm rolling with a total rolling reduction of 30% or more is performed.
(12) The method for producing an easily formable magnesium alloy sheet according to any one of (1) to (11), wherein annealing is performed by heat treatment after hot / warm rolling.
(13) The method for producing an easily formable magnesium alloy sheet according to (12), wherein recrystallization accompanied by a new arrangement of grain boundaries is caused by annealing by heat treatment.
(14) The method for producing an easily formable magnesium alloy sheet according to (12) or (13), wherein the sample temperature during annealing is 260 ° C to 450 ° C and the holding time is 10 minutes to 3 hours.
(15) The method for producing an easily formable magnesium alloy sheet according to any one of (12) to (14), wherein the sample temperature during annealing is 300 ° C to 400 ° C and the holding time is 10 minutes to 3 hours. .
(16) Easy molding characterized by having a Li content of less than 0.1% by mass and having poles in the plate width direction of the (0002) plane texture as measured by XRD method (Schulz reflection method) Magnesium alloy sheet.
(17) one or more light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm) and Zn, and the total amount of light rare earth elements is 0.01 to 1.0 mass%, Zn Is made of a magnesium alloy that contains impurities that are inevitably mixed in, and is measured by the XRD method (Schulz reflection method). An easily formable magnesium alloy sheet having poles in the sheet width direction of the texture.
(18) The method for producing an easily formable magnesium alloy sheet according to (17), wherein the total amount of Y and / or Sc is 0.5% by mass or less.
(19) The easily formable magnesium alloy sheet according to any one of (17) to (18), wherein the total amount of light rare earth elements is 0.01 to 0.7 mass%.
(20) The easy molding as described in any one of (17) to (19) above, wherein a rare earth element mixture (Misch metal: Mm) containing light rare earth elements as main components is used as the light rare earth elements. Magnesium alloy sheet.
(21) It contains Ca and Zn instead of light rare earth elements, the total amount of Ca is 0.01 to 0.6% by mass, the total amount of Zn is 0.4 to 2.6% by mass, Easily characterized in that it consists of a magnesium alloy that contains impurities that are inevitably mixed, and has poles in the plate width direction of the (0002) plane texture as measured by the XRD method (Schulz reflection method). Formable magnesium alloy sheet.
(22) The easily formable magnesium alloy sheet according to (21), wherein the total amount of Ca is 0.01 to 0.3% by mass.
(23) The easily formable magnesium alloy sheet according to (21) or (22), wherein Al having a total amount of 0.01 to 2.0% by mass is added.
(24) The easily formable magnesium alloy sheet according to any one of (17) to (23), wherein Mn and / or Zr having a total amount of 0.01 to 0.8 mass% is added. Production method.
(25) The method for producing an easily formable magnesium alloy sheet according to (24), wherein the total amount of Mn and / or Zr is 0.01 to 0.5 mass%.
(26) The easily formable magnesium alloy sheet according to any one of (16) to (25), wherein the Erichsen value is at least 8.0 or more at normal temperature (30 ° C).
(27) A magnesium alloy press-molded body comprising the molded body of the easily formable magnesium alloy sheet according to any one of (16) to (26).
(28) The magnesium alloy press-molded body according to (27), which shows a texture having poles on the (0002) plane in the plate width direction.
(29) A magnesium alloy member comprising the magnesium alloy press-molded body described in (27) or (28).
次に、本発明について更に詳細に説明する。
本発明は、常温（３０℃）で、エリクセン値が８．０以上の優れた成形性を有する易成形性マグネシウム合金板材を製造する方法であって、軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、及びＺｎを含み、軽希土類元素の総量が０．０１〜１．０質量％、好ましくは０．０１〜０．７質量％の範囲であり、Ｚｎの総量が０．４〜２．６質量％の範囲であり、適宜、０．０１〜０．８質量％、好ましくは０．０１〜０．５質量％の範囲のＭｎ及び／又はＺｒを含むものであり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金を、適当な条件で熱間・温間圧延し、適当な条件で熱処理に供することを特徴とするものである。本発明において、エリクセン値が８．０以上とは、エリクセン値が少なくても８．０の値であることを意味する。
Next, the present invention will be described in more detail.
The present invention is a method for producing an easily moldable magnesium alloy sheet having excellent formability having an Erichsen value of 8.0 or more at room temperature (30 ° C.), and comprises a light rare earth element (Y, Sc, La, Ce). , Pr, Nd, Sm) and Zn, and the total amount of light rare earth elements is in the range of 0.01 to 1.0% by mass, preferably 0.01 to 0.7% by mass. The total amount of is in the range of 0.4 to 2.6% by mass, suitably 0.01 to 0.8% by mass, preferably 0.01 to 0.5% by mass of Mn and / or Zr. In addition, a magnesium alloy constituted by containing impurities that are inevitably mixed is subjected to hot / warm rolling under appropriate conditions and subjected to heat treatment under appropriate conditions. In the present invention, the Eriksen value of 8.0 or more means that the Eriksen value is at least 8.0.
また、本発明は、常温（３０℃）で、エリクセン値が８．０以上の優れた成形性を有する易成形性マグネシウム合金板材を製造する方法であって、Ｃａ、及びＺｎを含み、Ｃａの総量が０．０１〜０．６質量％、好ましくは０．０１〜０．３質量％の範囲、Ｚｎの総量が０．４〜２．６質量％の範囲であり、必要に応じて、Ｍｎ及び／又はＺｒを０．０１〜０．８質量％、好ましくは０．０１〜０．５質量％の範囲、Ａｌを０．０１〜２．０質量％の範囲含み、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金を、適当な条件で熱間・温間圧延し、適当な条件で焼鈍することを特徴とするものである。 Further, the present invention is a method for producing an easily formable magnesium alloy sheet having excellent formability having an Erichsen value of 8.0 or more at room temperature (30 ° C.), comprising Ca and Zn, The total amount is in the range of 0.01 to 0.6% by mass, preferably in the range of 0.01 to 0.3% by mass, and the total amount of Zn is in the range of 0.4 to 2.6% by mass. And / or Zr is included in the range of 0.01 to 0.8% by mass, preferably in the range of 0.01 to 0.5% by mass, Al in the range of 0.01 to 2.0% by mass, and inevitably mixed. A magnesium alloy constituted by containing impurities is hot and warm rolled under appropriate conditions and annealed under appropriate conditions.
また、本発明は、上記製造方法で作製した易成形性マグネシウム合金板材であって、軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、及びＺｎを含み、軽希土類元素の総量が０．０１〜１．０質量％、好ましくは０．０１〜０．７質量％の範囲であり、Ｚｎの総量が０．４〜２．６質量％の範囲であり、適宜、０．０１〜０．８質量％、好ましくは０．０１〜０．５質量％の範囲のＭｎ及び／又はＺｒを含むものであり、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金からなり、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有し、常温（３０℃）で、エリクセン値が少なくとも８．０の成形性を示すことを特徴とするものである。 Further, the present invention is an easily moldable magnesium alloy sheet produced by the above production method, comprising one or more light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm), and Zn, The total amount of light rare earth elements is 0.01 to 1.0% by mass, preferably 0.01 to 0.7% by mass, and the total amount of Zn is 0.4 to 2.6% by mass, As appropriate, it contains Mn and / or Zr in the range of 0.01 to 0.8% by mass, preferably 0.01 to 0.5% by mass, and is configured by containing impurities that are inevitably mixed. A magnesium alloy having a pole in the plate width direction of the (0002) plane texture, measured at X-ray method (Schulz reflection method) and having an Erichsen value of at least 8.0 at room temperature (30 ° C.) It is characterized by showing sex.
また、本発明は、上記製造方法で作製した易成形性マグネシウム合金板材であって、Ｃａ、及びＺｎを含み、Ｃａの総量が０．０１〜０．６質量％、好ましくは０．０１〜０．３質量％の範囲、Ｚｎの総量が０．４〜２．６質量％の範囲であり、必要に応じて、Ｍｎ及び／又はＺｒを０．０１〜０．８質量％、好ましくは０．０１〜０．５質量％の範囲、Ａｌを０．０１〜２．０質量％の範囲含み、他に不可避に混入する不純物を含むことにより構成されるマグネシウム合金板材であり、ＸＲＤ法（シュルツの反射法）による測定で、（０００２）面集合組織の板幅方向に極を有し、常温（３０℃）で、エリクセン値が少なくとも８．０の成形性を示すことを特徴とするものである。 Further, the present invention is an easily moldable magnesium alloy sheet produced by the above production method, and contains Ca and Zn, and the total amount of Ca is 0.01 to 0.6% by mass, preferably 0.01 to 0. In the range of 0.3 mass%, the total amount of Zn is in the range of 0.4 to 2.6 mass%, and Mn and / or Zr is 0.01 to 0.8 mass%, preferably 0. It is a magnesium alloy plate material that includes a range of 01 to 0.5% by mass, Al in a range of 0.01 to 2.0% by mass, and additionally contains impurities that are inevitably mixed. It is characterized by having a pole in the plate width direction of the (0002) plane texture and exhibiting a moldability having an Erichsen value of at least 8.0 at room temperature (30 ° C.) as measured by a reflection method. .
また、本発明は、上記製造方法で作製した易成形性マグネシウム合金板材の成形体であって、板幅方向に（０００２）面の極を有する集合組織を示すマグネシウム合金製プレス成形体、及び該マグネシウム合金製プレス成形体からなるマグネシウム合金部材の点に特徴を有するものである。 In addition, the present invention is a compact of a readily formable magnesium alloy sheet produced by the above-described production method, a magnesium alloy press-molded body exhibiting a texture having a (0002) plane pole in the sheet width direction, and the It is characterized by the point of a magnesium alloy member made of a magnesium alloy press-formed body.
本発明者らは、以前の研究において、マグネシウム合金プレス成形体を、従来のプレス成形法よりも、低温で作製するための手段として、マグネシウムに、微量の軽希土類元素（Ｃｅ、Ｙ）を添加して、マグネシウムの成形性を向上させることを着想した。マグネシウムへの軽希土類元素の添加は、底面すべりと非底面すべりのＣＲＳＳの差を低減させ、結果として、圧延材の塑性異方性を低減し、圧延材に優れた成形性をもたらした。しかしながら、これらの合金のエリクセン値は、せいぜい４〜５程度であり、アルミニウム合金と比較して、低いものであった。 In the previous research, the inventors added a small amount of light rare earth elements (Ce, Y) to magnesium as a means for producing a magnesium alloy press-formed body at a lower temperature than the conventional press-forming method. The idea was to improve the moldability of magnesium. Addition of light rare earth elements to magnesium reduced the difference in CRSS between bottom and non-bottom slip, and as a result, reduced plastic anisotropy of the rolled material, resulting in excellent formability of the rolled material. However, the Erichsen value of these alloys is at most about 4 to 5, which is lower than that of aluminum alloys.
そこで、本発明者らは、上記マグネシウム合金の成形性を更に改善する手段として、Ｚｎを適当量添加し、更に、当該合金を、適当な条件で熱間・温間圧延することを着想し、詳細かつ系統的な実験を試みた。その結果の一つとして、図１に、後記する実施例で用いるＭｇ−１．５質量％Ｚｎ−０．２質量％Ｃｅ合金圧延材の（０００２）面集合組織を示す。 Therefore, the present inventors have conceived that, as a means for further improving the formability of the magnesium alloy, an appropriate amount of Zn is added, and the alloy is hot-rolled under appropriate conditions. A detailed and systematic experiment was attempted. As one of the results, FIG. 1 shows a (0002) plane texture of a Mg-1.5 mass% Zn-0.2 mass% Ce alloy rolled material used in examples described later.
３９０℃で圧延した試料には、焼鈍の有無にかかわらず、商用マグネシウム合金圧延材（ＡＺ３１Ｂ圧延材等）に特有の集合組織が現れた。すなわち、ＮＤ方向（垂直方向）からＲＤ方向（圧延方向）に、約３０°回転した付近に、（０００２）面の極が現れ、ＲＤ方向に、（０００２）面が傾いた分布を示した。 In the sample rolled at 390 ° C., a texture specific to a commercial magnesium alloy rolled material (such as AZ31B rolled material) appeared regardless of the presence or absence of annealing. That is, the pole of the (0002) plane appeared in the vicinity rotated about 30 ° from the ND direction (vertical direction) to the RD direction (rolling direction), and the (0002) plane was inclined in the RD direction.
それに対して、４５０℃で圧延し、更に、３５０℃（９０分）で焼鈍した試料の集合組織には、ＮＤ方向からＴＤ方向（板幅方向）に約３０°回転した付近に、（０００２）面の極が現れ、ＲＤ方向よりもＴＤ方向に、（０００２）面が傾いた分布を示した。ＴＤ方向に広がりを持った集合組織を示すＭｇ−１．５質量％Ｚｎ−０．２質量％Ｃｅ合金圧延材（４５０℃圧延材）は、商用マグネシウム合金よりも、ランダムな集合組織を有するため、成形性は、著しく向上した。 On the other hand, in the texture of the sample rolled at 450 ° C. and annealed at 350 ° C. (90 minutes), in the vicinity rotated about 30 ° from the ND direction to the TD direction (plate width direction), (0002) The poles of the surface appeared and showed a distribution in which the (0002) surface was inclined in the TD direction rather than the RD direction. The Mg-1.5 mass% Zn-0.2 mass% Ce alloy rolled material (450 ° C. rolled material) showing a texture having a spread in the TD direction has a random texture than a commercial magnesium alloy. The moldability was remarkably improved.
軽希土類元素と亜鉛を添加したマグネシウム合金を、熱間圧延すると、商用マグネシウム合金とは全く異なる集合組織が現れる原因の一つとして、ｃ／ａ比の変化が挙げられる。図１の４５０℃圧延材の焼鈍後の集合組織は、Ｍｇ−Ｌｉ合金の（０００２）面集合組織と酷似している（文献：Ｈ．Ｔａｋｕｄａ ｅｔ ａｌ．：Ｍａｔｅｒ．Ｓｃｉ．Ｅｎｇ．Ａ Ｖｏｌ．２７１（１９９９）２５１−２５６）。 When a magnesium alloy to which a light rare earth element and zinc are added is hot-rolled, one of the causes that a completely different texture from that of a commercial magnesium alloy appears is a change in the c / a ratio. The texture after annealing of the 450 ° C. rolled material of FIG. 1 is very similar to the (0002) plane texture of the Mg—Li alloy (reference: H. Takuda et al .: Mater. Sci. Eng. A Vol. 271 (1999) 251-256).
Ｍｇ−１８ａｔ％Ｌｉ合金のｃ／ａ比（常温）は、１．６０８６であり、純Ｍｇ（１．６２３６）よりも著しく低い値を取る（非特許文献１）。それゆえに、軽希土類元素類とＺｎの添加が、マグネシウム合金のｃ／ａ比に影響を及ぼし、結果として、図１に示す集合組織が発現すると考えることができる。 The c / a ratio (normal temperature) of the Mg-18 at% Li alloy is 1.6086, which is significantly lower than pure Mg (1.6236) (Non-patent Document 1). Therefore, it can be considered that the addition of light rare earth elements and Zn affects the c / a ratio of the magnesium alloy, and as a result, the texture shown in FIG. 1 appears.
結果的に、本発明者らは、マグネシウムに、規定量の軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、Ｚｎ、及び必要により、Ｍｎ、Ｚｒを添加した合金を、適当な条件で熱間・温間圧延し、更に、適当な熱処理に供することにより、板材の（０００２）面集合組織に板幅方向に極を発現させ、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する成形性及び延性を有する易成形性マグネシウム合金板材及びその加工材を作製することに成功した。 As a result, the present inventors added one or more kinds of light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm), Zn, and, if necessary, Mn and Zr to magnesium. The obtained alloy is hot and warm rolled under appropriate conditions, and further subjected to an appropriate heat treatment to develop a pole in the (0002) plane texture of the plate material in the plate width direction, at room temperature (30 ° C.). The present inventors have succeeded in producing an easily formable magnesium alloy sheet material and a processed material thereof that have the same formability and ductility as aluminum alloys.
すなわち、本発明者らは、具体的には、Ｌｉを利用せずに、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する、優れた成形性、すなわち、エリクセン値が８．０以上の成形性を有する易成形性マグネシウム合金板材を作製することに成功した。 That is, the present inventors specifically have excellent formability, that is, an Erichsen value equal to or higher than that of an aluminum alloy at room temperature (30 ° C.) without using Li. We succeeded in producing an easily formable magnesium alloy sheet having the following formability.
本発明者らは、更なる詳細かつ系統的な実験を試みた結果、規定量のＣａ、Ｚｎ、及び必要により、Ａｌ、Ｍｎ、Ｚｒを添加した合金を、適当な条件で熱間・温間圧延し、更に、適当な条件で熱処理を行うことにより、希土類元素を添加した合金とほぼ同じ集合組織が形成され、優れた常温成形性が発現することを発見した。 As a result of further detailed and systematic experiments, the inventors of the present invention have used hot and warm alloys under appropriate conditions for alloys containing a specified amount of Ca, Zn and, if necessary, Al, Mn, and Zr. It was discovered that by rolling and further heat-treating under appropriate conditions, almost the same texture as that of the alloy added with rare earth elements was formed, and excellent room temperature formability was exhibited.
その結果の一つとして、図２（ｄ）に、後記する実施例で用いるＭｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の（０００２）面集合組織を示す。本試料は、厚み５ｍｍの試料を、試料温度４５０℃で、１ｍｍまで圧延し、３５０℃（９０分）の熱処理に供した試料の結果である。 As one of the results, FIG. 2 (d) shows the (0002) plane texture of the Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material used in the examples described later. This sample is a result of a sample obtained by rolling a sample having a thickness of 5 mm to 1 mm at a sample temperature of 450 ° C. and subjecting it to a heat treatment at 350 ° C. (90 minutes).
Ｍｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の集合組織には、ＮＤ方向からＴＤ方向（板幅方向）に約３０°回転した付近に、（０００２）面の極が現れ、ＲＤ方向よりもＴＤ方向に、（０００２）面が傾いた分布を示した。ＴＤ方向の広がりを持った集合組織を示すＭｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材は、商用マグネシウム合金よりもランダムな集合組織を有するため、成形性は、著しく向上した。 In the texture of the Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material, there is a pole on the (0002) plane in the vicinity of about 30 ° rotation from the ND direction to the TD direction (plate width direction). It appeared and showed a distribution in which the (0002) plane was inclined in the TD direction rather than the RD direction. Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material showing a texture having a spread in the TD direction has a random texture than commercial magnesium alloys, so the formability is remarkably improved. did.
その結果、本発明者らは、マグネシウムに、規定量のＣａ、Ｚｎ、及び必要により、Ｍｎ、Ｚｒ，Ａｌを添加した合金を、適当な条件で熱間・温間圧延し、更に、適当な条件で熱処理を行うことにより、板材の（０００２）面集合組織に、板幅方向に極を発現させ、常温（３０℃）で、アルミニウム合金に匹敵する成形性及び延性を有するマグネシウム合金板材を作製することに成功した。 As a result, the inventors of the present invention hot and warm rolled an alloy obtained by adding a specified amount of Ca, Zn and, if necessary, Mn, Zr, and Al to magnesium under appropriate conditions. By performing heat treatment under the conditions, a magnesium alloy plate material having formability and ductility comparable to an aluminum alloy is produced at room temperature (30 ° C) by causing the (0002) plane texture of the plate material to exhibit poles in the plate width direction. Succeeded in doing.
すなわち、本発明者らは、具体的には、Ｌｉや軽希土類元素を利用せずに、常温（３０℃）で、アルミニウム合金に匹敵する易成形性、すなわち、エリクセン値が８．０以上の成形性を有するマグネシウム合金板材を作製することに成功した。 That is, the inventors specifically did not use Li or a light rare earth element, and at room temperature (30 ° C.), easy formability comparable to that of an aluminum alloy, that is, an Erichsen value of 8.0 or more. A magnesium alloy sheet with formability was successfully produced.
次に、本発明を発現させるために必要な合金組成について詳細に説明する。はじめに、軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上を添加したマグネシウム合金の合金組成について説明する。本発明において、軽希土類元素の１種以上とは、上記元素の１種又は２種以上であることを意味する。 Next, the alloy composition necessary for developing the present invention will be described in detail. First, an alloy composition of a magnesium alloy to which one or more light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm) are added will be described. In the present invention, one or more light rare earth elements means one or more of the above elements.
Ｃｅ、Ｌａ、Ｎｄ、Ｐｒ、Ｓｍは、マグネシウムに常温で殆ど固溶せず（文献：Ｌ．Ｌ．Ｒｏｋｈｌｉｎ：“Ｍａｇｎｅｓｉｕｍ Ａｌｌｏｙｓ Ｃｏｎｔａｉｎｉｎｇ Ｒａｒｅ Ｅａｒｔｈ Ｍｅｔａｌｓ”，（Ｔａｙｌｏｒ ＆ Ｆｒａｎｃｉｓ，Ｌｏｎｄｏｎ，２００３）ｐｐ．１８−６７）、固溶硬化の影響は少ない。 Ce, La, Nd, Pr, and Sm hardly dissolve in magnesium at room temperature (Reference: LL Rokhlin: “Magnesium Alloys Containing Rare Earth Metals”, (Taylor & Francis, London, 2003), pp. 18). -67) The effect of solid solution hardening is small.
一方、Ｃｅ、Ｌａ、Ｎｄ、Ｐｒ、Ｓｍの１種以上を１．０質量％以上添加すると、軽希土類元素が析出し、成形性・延性を低下させるため、本発明では、Ｃｅ、Ｌａ、Ｎｄ、Ｐｒ、Ｓｍの１種以上の添加量は、１．０質量％以下、好ましくは０．７質量％以下に設定すべきである。 On the other hand, when one or more of Ce, La, Nd, Pr, and Sm is added in an amount of 1.0% by mass or more, light rare earth elements are precipitated and formability and ductility are lowered. In the present invention, Ce, La, Nd The addition amount of one or more of Pr, Sm should be set to 1.0% by mass or less, preferably 0.7% by mass or less.
Ｙ、Ｓｃは、マグネシウムに、常温で２質量％以上固溶する（文献：Ｌ．Ｌ．Ｒｏｋｈｋｉｎ：“Ｍａｇｎｅｉｕｍ Ａｌｌｏｙｓ Ｃｏｎｔａｉｎｉｎｇ Ｒａｒｅ Ｅａｒｔｈ Ｍｅｔａｌｓ”，（Ｔａｙｌｏｒ ＆ Ｆｒａｎｃｉｓ，Ｌｏｎｄｏｎ，２００３）ｐｐ．１８−６７）。しかし、Ｙ及び／又はＳｃを、０．５質量％よりも多く添加すると、固溶硬化の影響が強くなり、成形性及び延性に悪影響を及ぼす。それゆえに、本発明では、Ｙ及び／又はＳｃの添加量は、０．５質量％以下に設定すべきである。 Y and Sc are solid-dissolved in magnesium at 2% by mass or more at normal temperature (Reference: LL Rokhkin: “Magneium Alloys Containing Rare Earth Metals”, (Taylor & Francis, London, 2003) pp. 18-67). . However, when Y and / or Sc is added in an amount of more than 0.5% by mass, the effect of solid solution hardening becomes strong, which adversely affects moldability and ductility. Therefore, in this invention, the addition amount of Y and / or Sc should be set to 0.5 mass% or less.
なお、軽希土類元素単体と比較して、入手が容易であるミッシュメタル（Ｍｍ：軽希土類元素を主成分とする希土類元素群）を代用品として利用しても、同様の効果が発現することを実験により確認している。本発明では、該ミッシュメタル（Ｍｍ）を、「Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｙ、Ｓｃのいずれかを主成分とする希土類元素群」として、それらと同等のものとして取り扱うこととする。 It should be noted that the same effect can be obtained even if misch metal (Mm: rare earth element group mainly composed of light rare earth elements), which is easily available, is used as a substitute compared to light rare earth elements alone. Confirmed by experiment. In the present invention, the misch metal (Mm) is treated as “a rare earth element group mainly containing any one of La, Ce, Pr, Nd, Sm, Y, and Sc” as equivalent to them. .
前述の通り、Ｃｅ、Ｌａ、Ｎｄ、Ｐｒ、Ｓｍは、常温で、Ｍｇに固溶せず、その１種以上を１．０質量％以上添加すると、析出物として、素材の成形性に悪影響を及ぼす。一方、Ｙ、Ｓｃは、常温で、Ｍｇに固溶するが、その１種以上を０．５質量％以上添加すると、固溶硬化の影響が無視できず、素材の成形性に悪影響を及ぼす。なお、それぞれの添加元素が素材の成形性に及ぼす因子は、独立しており、軽希土類元素群を合わせて、添加することができる。 As described above, Ce, La, Nd, Pr, and Sm are not dissolved in Mg at room temperature, and when one or more of them are added in an amount of 1.0% by mass or more, they adversely affect the moldability of the material as precipitates. Effect. On the other hand, Y and Sc are solid-dissolved in Mg at room temperature, but if one or more of them are added in an amount of 0.5% by mass or more, the effect of solid solution hardening cannot be ignored, and the material moldability is adversely affected. In addition, the factor which each additive element exerts on the moldability of a raw material is independent, and can add together a light rare earth element group.
Ｚｎは、マグネシウムに、常温で、２〜３質量％固溶する（文献：Ｂｉｎａｒｙ ａｌｌｏｙ ｐｈａｓｅ ｄｉａｇｒａｍｓ，Ｔ．Ｂ．Ｍａｓｓａｌｓｋｉ（ｅｄ．）（Ａｍｅｒｉｃａｎ Ｓｏｃｉｅｔｙ ｆｏｒ Ｍｅｔａｌｓ，Ｍｅｔａｌｓ Ｐａｒｋ，Ｏｈｉｏ，１９８６），ｐｐ．２５７１−２５７２）。 Zn is dissolved in magnesium at 2-3% by mass at room temperature (Reference: binary alloy phase diagrams, TB Massalski (ed.) (American Society for Metals, Metals Park, Ohio, 1986), pp. 2571-2572).
３質量％程度のＺｎを添加すると、析出物が形成され、成形性・延性が低下するため、添加量は、２．６質量％以下と設定すべきである。また、Ｚｎ添加の影響を顕在化させるためには、０．４質量％以上の添加が必要である。 When about 3% by mass of Zn is added, precipitates are formed and the moldability and ductility are lowered. Therefore, the addition amount should be set to 2.6% by mass or less. Moreover, in order to reveal the influence of Zn addition, 0.4 mass% or more needs to be added.
Ｍｎ、Ｚｒの添加は、マグネシウム合金板材の結晶粒径を微細にするため、材料強化に有効である。一方、Ｍｎ、Ｚｒを一定以上添加すると、粗大なＭｎ、Ｚｒ相、もしくはＭｎ、Ｚｒ基金属間化合物相が内部に形成され、材料の成形性及び延性が劣化する。それゆえに、本発明では、Ｍｎ、Ｚｒの添加量は、０．０１〜０．８質量％、より好ましくは０．０１〜０．５質量％に設定することが好ましい。 The addition of Mn and Zr is effective for strengthening the material because the crystal grain size of the magnesium alloy sheet is made fine. On the other hand, when Mn and Zr are added more than a certain amount, coarse Mn and Zr phases or Mn and Zr-based intermetallic compound phases are formed inside, and the formability and ductility of the material deteriorate. Therefore, in this invention, it is preferable to set the addition amount of Mn and Zr to 0.01-0.8 mass%, More preferably, it sets to 0.01-0.5 mass%.
次に、軽希土類元素の代わりに、Ｃａを添加したマグネシウム合金の合金組成について説明する。Ｃａは、マグネシウムに、常温で、殆ど固溶せず［文献：Ｂｉｎａｒｙ ａｌｌｏｙ ｐｈａｓｅ ｄｉａｇｒａｍｓ，Ｔ．Ｂ．Ｍａｓｓａｌｓｋｉ（ｅｄ．）（Ａｍｅｒｉｃａｎ Ｓｏｃｉｅｔｙ ｆｏｒ Ｍｅｔａｌｓ，Ｍｅｔａｌｓ Ｐａｒｋ，Ｏｈｉｏ，１９８６），ｐｐ．９２５−９２８］、固溶硬化の影響は少ない。 Next, the alloy composition of the magnesium alloy to which Ca is added instead of the light rare earth element will be described. Ca hardly dissolves in magnesium at room temperature [Literature: Binary alloy phase diagrams, T. et al. B. Massalski (ed.) (American Society for Metals, Metals Park, Ohio, 1986), pp. 925-928], the effect of solid solution hardening is small.
一方、０．６質量％以上（あるいは０．３質量％以上）のＣａを添加すると、金属間化合物のＭｇ２Ｃａ等が析出し、圧延性、成形性、延性を低下させるため、Ｃａの添加量は、０．６質量％以下、好ましくは０．３質量％以下と設定すべきである。また、Ｃａ添加の影響を顕在化させるためには、０．０１質量％以上の添加が必要である。 On the other hand, when 0.6 mass% or more (or 0.3 mass% or more) of Ca is added, Mg 2 Ca or the like of the intermetallic compound is precipitated, and the rollability, formability, and ductility are reduced. The amount should be set to 0.6% by weight or less, preferably 0.3% by weight or less. Moreover, in order to reveal the influence of Ca addition, addition of 0.01 mass% or more is required.
Ｚｎは、マグネシウムに、常温で、２〜３質量％固溶する［文献：Ｂｉｎａｒｙ ａｌｌｏｙ ｐｈａｓｅ ｄｉａｇｒａｍｓ，Ｔ．Ｂ．Ｍａｓｓａｌｓｋｉ（ｅｄ．）（Ａｍｅｒｉｃａｎ Ｓｏｃｉｅｔｙ ｆｏｒ Ｍｅｔａｌｓ，Ｍｅｔａｌｓ Ｐａｒｋ，Ｏｈｉｏ，１９８６），ｐｐ．２５７１−２５７２］。 Zn is dissolved in magnesium at 2-3% by mass at room temperature [Reference: Binary alloy phase diagrams, T. et al. B. Massalski (ed.) (American Society for Metals, Metals Park, Ohio, 1986), pp. 2571-2572].
３質量％程度のＺｎを添加すると、析出物が形成され、成形性・延性が低下するため、Ｚｎの添加量は、２．６質量％以下と設定すべきである。また、Ｚｎ添加の影響を顕在化させるためには、０．４質量％以上の添加が必要である。 When about 3% by mass of Zn is added, precipitates are formed and the moldability and ductility are lowered. Therefore, the amount of Zn added should be set to 2.6% by mass or less. Moreover, in order to reveal the influence of Zn addition, 0.4 mass% or more needs to be added.
Ｍｎ、Ｚｒの添加は、マグネシウム合金板材の結晶粒径を微細にするため、材料強化に有効である。一方、Ｍｎ、Ｚｒを一定以上添加すると、粗大なＭｎ、Ｚｒ相、もしくはＭｎ、Ｚｒ基金属間化合物相が内部に形成され、材料の成形性及び延性が劣化する。それゆえに、本発明では、Ｍｎ，Ｚｒの添加量は、０．０１〜０．８質量％、より好ましくは０．０１〜０．５質量％に設定することが好ましい。 The addition of Mn and Zr is effective for strengthening the material because the crystal grain size of the magnesium alloy sheet is made fine. On the other hand, when Mn and Zr are added more than a certain amount, coarse Mn and Zr phases or Mn and Zr-based intermetallic compound phases are formed inside, and the formability and ductility of the material deteriorate. Therefore, in the present invention, the amount of Mn and Zr added is preferably set to 0.01 to 0.8 mass%, more preferably 0.01 to 0.5 mass%.
Ａｌは、マグネシウムに、常温で、１〜２質量％固溶し［文献：Ｂｉｎａｒｙ ａｌｌｏｙ ｐｈａｓｅ ｄｉａｇｒａｍｓ，Ｔ．Ｂ．Ｍａｓｓａｌｓｋｉ（ｅｄ．）（Ａｍｅｒｉｃａｎ Ｓｏｃｉｅｔｙ ｆｏｒ Ｍｅｔａｌｓ，Ｍｅｔａｌｓ Ｐａｒｋ，Ｏｈｉｏ，１９８６），ｐｐ．１６９−１７１］、固溶強化を手段とした材料強化に有効である。 Al is dissolved in magnesium at 1 to 2 mass% at room temperature [Reference: Binary alloy phase diagrams, T .; B. Massalski (ed.) (American Society for Metals, Metals Park, Ohio, 1986), pp. 169-171], which is effective for material strengthening using solid solution strengthening as a means.
しかし、Ａｌを一定以上添加すると、Ｃａ、Ｚｎ添加の効果が無くなり、板材の（０００２）面集合組織に、板幅方向の極が発現しなくなるため、Ａｌの添加量は、２．０質量％以下と設定すべきである。なお、軽希土類元素を添加した合金にＡｌを添加すると、Ａｌ−ＲＥ（希土類元素）系金属間化合物が形成し、常温成形性が劣化する。そのため、軽希土類元素を添加した合金へのＡｌの添加は、避けるべきである。 However, if Al is added more than a certain amount, the effect of adding Ca and Zn is lost, and the pole in the plate width direction does not appear in the (0002) plane texture of the plate material. Should be set as follows. If Al is added to an alloy to which a light rare earth element is added, an Al-RE (rare earth element) -based intermetallic compound is formed, and the room temperature formability deteriorates. Therefore, addition of Al to an alloy to which a light rare earth element is added should be avoided.
次に、上記組成により構成されるマグネシウム合金の圧延条件及び焼鈍条件について説明する。上記組成により構成されるマグネシウム合金板材の成形性を向上させるためには、試料を、熱間・温間圧延等の熱間・温間加工に供し、更に、焼鈍を行うことにより、板幅方向に（０００２）面の極が現れる集合組織を作り込む必要がある。板幅方向に（０００２）面の極が現れる集合組織を作り込むために必要とされる加工条件は、添加する元素（軽希土類元素、Ｃａ）の種類により異なる。 Next, the rolling conditions and annealing conditions of the magnesium alloy comprised by the said composition are demonstrated. In order to improve the formability of the magnesium alloy sheet composed of the above composition, the sample is subjected to hot / warm processing such as hot / warm rolling, and further annealed, so that the sheet width direction It is necessary to create a texture in which the poles of the (0002) plane appear. The processing conditions required to create a texture in which the poles of the (0002) plane appear in the plate width direction vary depending on the type of element (light rare earth element, Ca) to be added.
図１に示す通り、Ｍｇ−Ｚｎ−Ｃｅ系合金においては、試料を、高温（４５０℃程度）に加熱した上で、熱間・温間圧延を行い、更に、焼鈍を行うと、板幅方向に（０００２）面の極が現れる集合組織が発現する。一方、試料温度３９０℃で、圧延を実施すると、焼鈍を行っても、板幅方向に（０００２）面の極は現れず、成形性は、改善されない。なお、この現象は、Ｍｇ−Ｚｎ−Ｌａ系合金においても確認されている（後記する、実施例１７、比較例６を参照）。 As shown in FIG. 1, in the Mg—Zn—Ce-based alloy, the sample is heated to a high temperature (about 450 ° C.), then hot / warm rolled, and further annealed to obtain a sheet width direction. A texture appears in which the poles of the (0002) plane appear. On the other hand, when rolling is performed at a sample temperature of 390 ° C., even if annealing is performed, no pole on the (0002) plane appears in the sheet width direction, and the formability is not improved. This phenomenon has also been confirmed in Mg—Zn—La alloys (see Example 17 and Comparative Example 6 described later).
このように、Ｍｇ−Ｚｎ−Ｃｅ系合金及びＭｇ−Ｚｎ−Ｌａ系合金の（０００２）面集合組織に、板幅方向の極を発現させるためには、４００℃以上の試料温度で、熱間・温間加工を行う必要がある。なお、Ｍｇ−Ｚｎ−Ｃｅ系合金及びＭｇ−Ｚｎ−Ｌａ系合金に好適な試料温度は、ロール加熱機構の有無により若干異なる。ロールに、加熱機構があり、ロール表面を、２００℃程度に加熱できる場合は、圧延時の試料温度を、低く設定することができる。具体的には、試料温度を４００〜４３０℃程度に設定すると良い。 As described above, in order to develop the pole in the plate width direction in the (0002) plane texture of the Mg—Zn—Ce based alloy and the Mg—Zn—La based alloy, the sample is heated at a sample temperature of 400 ° C. or higher.・ Warm machining is required. Note that the sample temperature suitable for the Mg—Zn—Ce alloy and the Mg—Zn—La alloy varies slightly depending on the presence or absence of a roll heating mechanism. When the roll has a heating mechanism and the roll surface can be heated to about 200 ° C., the sample temperature during rolling can be set low. Specifically, the sample temperature may be set to about 400 to 430 ° C.
ロールに、加熱機構が無く、ロール表面温度が、常温〜１００℃である場合は、圧延前の試料温度を４３０〜４８０℃程度に設定する必要がある。なお、圧延前の試料温度を、５００℃以上に設定すると、加熱時に、結晶粒の異常粒成長が起こり、圧延後の試料組織が不均一となるため、避けるべきである。 When the roll has no heating mechanism and the roll surface temperature is from room temperature to 100 ° C, it is necessary to set the sample temperature before rolling to about 430 to 480 ° C. If the sample temperature before rolling is set to 500 ° C. or higher, abnormal grain growth of crystal grains occurs during heating, and the sample structure after rolling becomes non-uniform, which should be avoided.
一方、他の軽希土類元素（Ｙ、Ｓｃ、Ｎｄ、Ｐｒ、Ｓｍ）の１種以上を添加したマグネシウム合金の（０００２）面集合組織には、比較的低温（４００℃未満）で、温間加工を行っても、板幅方向に（０００２）面の極が現れる。また、軽希土類元素の代わりに、Ｃａを添加したマグネシウム合金に関しても、比較的低温（４００℃未満）で、温間加工を行っても、板幅方向に（０００２）面の極が現れる。 On the other hand, the (0002) plane texture of a magnesium alloy to which one or more of other light rare earth elements (Y, Sc, Nd, Pr, Sm) are added is warm-worked at a relatively low temperature (less than 400 ° C). Even if it performs, the pole of the (0002) plane appears in the plate width direction. Further, regarding a magnesium alloy to which Ca is added instead of a light rare earth element, a pole on the (0002) plane appears in the plate width direction even when warm working is performed at a relatively low temperature (less than 400 ° C.).
そのため、Ｃｅ、Ｌａ以外の軽希土類元素を主に添加したマグネシウム合金、及び、Ｃａを添加したマグネシウム合金に関しては、圧延温度の制約は無く、熱間・温間圧延を実施することにより、成形性の改善に資する集合組織を作り込むことができる。 Therefore, regarding magnesium alloys mainly containing light rare earth elements other than Ce and La, and magnesium alloys to which Ca is added, there is no restriction on rolling temperature, and formability can be achieved by carrying out hot / warm rolling. It is possible to build a collective organization that contributes to the improvement of
上記組成により構成されるマグネシウム合金板材の（０００２）面集合組織に、板幅方向の極を発現させるためには、一定以上の加工を行い、十分な歪みエネルギーを試料に投入する必要がある。図２に、後記するＭｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の（０００２）面集合組織を示す。 In order to make the (0002) plane texture of the magnesium alloy plate material having the above composition develop a pole in the plate width direction, it is necessary to perform a certain amount of processing and to input sufficient strain energy to the sample. FIG. 2 shows a (0002) plane texture of a Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material described later.
本試料は、厚み５ｍｍの試料を、試料温度４５０℃もしくは３５０℃で、厚み４ｍｍ（圧下率２０％）もしくは１ｍｍ（圧下率８０％）まで圧延し、３５０℃（９０分）の熱処理に供した試料の結果である。圧下率２０％の圧延を行った試料の（０００２）面集合組織には、試料温度に関係無く、板幅方向に明確な極は現れない。 In this sample, a sample having a thickness of 5 mm was rolled at a sample temperature of 450 ° C. or 350 ° C. to a thickness of 4 mm (rolling rate 20%) or 1 mm (rolling rate 80%) and subjected to heat treatment at 350 ° C. (90 minutes). It is a result of a sample. In the (0002) plane texture of the sample that has been rolled at a reduction rate of 20%, no clear pole appears in the plate width direction regardless of the sample temperature.
一方、圧下率の高い圧延（圧下率８０％）を行った試料には、板幅方向に明確な極が発現する。このように、集合組織を改質するためには、少なくとも圧下率３０％以上の圧延、より好ましくは５０％以上の圧延を行い、試料に十分な歪みエネルギーを投入する必要がある。 On the other hand, a clear pole appears in the sheet width direction in a sample subjected to rolling with a high reduction ratio (80% reduction ratio). Thus, in order to modify the texture, it is necessary to perform rolling at a rolling reduction of 30% or more, more preferably rolling at 50% or more, and to input sufficient strain energy to the sample.
上記組成により構成されるマグネシウム合金板材の（０００２）面集合組織に、板幅方向の極を発現させるためには、上記条件で熱間・温間圧延を行った試料に、適当な条件の熱処理を行うことが不可欠である。図３に、後記するＭｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の熱処理前後の（０００２）面集合組織を示す。図３に示す通り、焼鈍前の試料には、圧延温度（３９０℃及び４５０℃）に関係なく、板幅方向に、（０００２）面の極は現れない。 In order to develop a pole in the sheet width direction in the (0002) plane texture of a magnesium alloy sheet composed of the above composition, a sample subjected to hot / warm rolling under the above conditions is subjected to heat treatment under appropriate conditions. It is essential to do. FIG. 3 shows the (0002) plane texture before and after heat treatment of the Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material described later. As shown in FIG. 3, no pole on the (0002) plane appears in the plate width direction in the sample before annealing regardless of the rolling temperature (390 ° C. and 450 ° C.).
また、低温（２５０℃）で焼鈍を行っても、板幅方向に、（０００２）面の極は現れない。すなわち、適当な条件、２６０℃、１０分以上、好ましくは３００℃以上、１０分以上で焼鈍を行い、粒界の新しい配列を伴う再結晶を起こさないと、板幅方向に、（０００２）面の極は現れず、優れた常温成形性は発現しない。しかし、４５０℃を越える温度で３時間以上の焼鈍を行うと、焼鈍中に異常粒成長が起こり、常温成形性は劣化する。そのため、焼鈍条件は、４５０℃以下、３時間未満に設定すべきである。 Further, even if annealing is performed at a low temperature (250 ° C.), no pole on the (0002) plane appears in the plate width direction. That is, if annealing is performed under appropriate conditions, 260 ° C., 10 minutes or more, preferably 300 ° C., 10 minutes or more, and recrystallization accompanied by a new arrangement of grain boundaries does not occur, No poles appear, and excellent room temperature moldability does not appear. However, if annealing is performed at a temperature exceeding 450 ° C. for 3 hours or more, abnormal grain growth occurs during annealing, and the room temperature formability deteriorates. Therefore, the annealing conditions should be set to 450 ° C. or less and less than 3 hours.
なお、粒界の新しい配列を伴う再結晶とは、焼鈍中に新たな大傾角粒界の発生を伴う再結晶を指し、大傾角粒界の発生を伴わない再結晶（いわゆる回復）とは区別される。一般的に、大傾角粒界の発生を伴う再結晶は、加工した金属を融点の約１／２以上の温度に加熱すると発現する。マグネシウムの融点は、６５０℃であるので、焼鈍中の粒成長を抑制しつつ、粒界の新しい配列を伴う再結晶を起こすためには、３００℃〜４００℃で、焼鈍を行うことが最も好ましい。 Note that recrystallization with a new arrangement of grain boundaries refers to recrystallization with the occurrence of new large-angle grain boundaries during annealing, and is distinct from recrystallization without the occurrence of large-angle grain boundaries (so-called recovery). Is done. In general, recrystallization accompanied by generation of a large-angle grain boundary appears when the processed metal is heated to a temperature of about ½ or more of the melting point. Since the melting point of magnesium is 650 ° C., it is most preferable to perform annealing at 300 ° C. to 400 ° C. in order to cause recrystallization accompanied by a new arrangement of grain boundaries while suppressing grain growth during annealing. .
上記本発明の要素を駆使して作製されたマグネシウム合金板材は、常温（３０℃）で、アルミニウム合金に匹敵する常温成形性、すなわち、エリクセン値が８．０以上の成形性を示す。ここでは、マグネシウム合金板材の成形性を表す指標として、エリクセン値を採用した。また、エリクセン試験は、ＪＩＳ Ｂ７７２９及びＪＩＳ Ｚ２２７４に準ずる試験を指す。 The magnesium alloy sheet produced by making full use of the above-described elements of the present invention exhibits room temperature formability comparable to an aluminum alloy at room temperature (30 ° C.), that is, formability with an Erichsen value of 8.0 or more. Here, the Erichsen value was adopted as an index representing the formability of the magnesium alloy sheet. The Eriksen test refers to a test according to JIS B7729 and JIS Z2274.
本発明により、次のような効果が奏される。
（１）マグネシウムに、規定量の軽希土類元素、Ｚｎ、及び必要によりＭｎ、Ｚｒを添加した合金を、熱間・温間圧延に供し、更に、適当な熱処理に供することにより、易成形性マグネシウム合金板材を作製することができる。
（２）マグネシウムに、規定量のＣａ、Ｚｎ、及び必要によりＡｌ、Ｍｎ、Ｚｒを添加した合金を、適当な条件で熱間・温間圧延に供し、更に、適当な条件で熱処理に供することにより、易成形性マグネシウム合金板材を作製することができる。
（３）得られた板材の（０００２）面集合組織には、板幅方向に極が現れ、Ｌｉを利用せずに、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する優れた成形性（常温でエリクセン値が８．０以上）が付与される。
（４）上記易成形性マグネシウム合金板材を成形してなるマグネシウム合金製プレス成形体を作製し、提供することができる。
（５）上記マグネシウム合金製プレス成形体からなる筐体等のマグネシウム合金製部材を作製し、提供することができる。
The present invention has the following effects.
(1) Magnesium, an alloy obtained by adding a specified amount of a light rare earth element, Zn, and optionally Mn and Zr, to hot and warm rolling, and further to an appropriate heat treatment, easily moldable magnesium An alloy sheet can be produced.
(2) An alloy obtained by adding a specified amount of Ca, Zn and, if necessary, Al, Mn, Zr to magnesium, is subjected to hot / warm rolling under appropriate conditions, and further subjected to heat treatment under appropriate conditions. Thus, an easily moldable magnesium alloy sheet can be produced.
(3) In the (0002) plane texture of the obtained plate material, poles appear in the width direction of the plate, and excellent molding that is equivalent to or comparable to an aluminum alloy at room temperature (30 ° C.) without using Li (Ericsen value is 8.0 or more at room temperature).
(4) A magnesium alloy press-molded body formed by molding the easily formable magnesium alloy sheet can be produced and provided.
(5) A magnesium alloy member such as a casing made of the magnesium alloy press-molded body can be produced and provided.
次に、本発明を実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these Examples.
実施例１〜３９及び比較例１〜１４
（１）軽希土類元素を含むマグネシウム合金板材の製造
高周波炉を用いて、純マグネシウムインゴットを溶解した後、軽希土類元素（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）、ミッシュメタル（Ｍｍ）、Ｚｎ、Ｍｎ、Ｚｒを適宜添加することにより、Ｍｇ合金を作製した。利用したＭｍの組成を表１に示す。
Examples 1-39 and Comparative Examples 1-14
(1) Manufacture of magnesium alloy sheet containing light rare earth elements After melting a pure magnesium ingot using a high frequency furnace, light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm), Misch metal (Mm) ), Zn, Mn, and Zr were appropriately added to prepare an Mg alloy. The composition of Mm used is shown in Table 1.
また、後記する表２に、Ｍｇ合金材料の組成を示す。上記マグネシウム合金（５０×３０×５０ｍｍ３）を、熱間押出し（押出し温度６７３Ｋ、押出し速度３ｍｍ／ｍｉｎ、押出し比６）に供し、押出し板材（断面積：５０×５ｍｍ２）を作製した。この押出し板材より、６０ｍｍ×５０ｍｍ×５ｍｍの試験片を切出し、それらの試験片を圧延に供した。 In addition, Table 2 described later shows the composition of the Mg alloy material. The magnesium alloy (50 × 30 × 50 mm 3 ) was subjected to hot extrusion (extrusion temperature 673K, extrusion speed 3 mm / min, extrusion ratio 6) to produce an extruded plate (cross-sectional area: 50 × 5 mm 2 ). From this extruded plate material, test pieces of 60 mm × 50 mm × 5 mm were cut out and subjected to rolling.
圧延時の試料温度は、３５０℃〜４５０℃とし、圧延速度を５ｍ／ｍｉｎ、１パス毎の圧下率を１５〜２０％に設定し、厚み５ｍｍの試料を１ｍｍまで圧延した。最後に、圧延材を、３５０℃で、９０分の熱処理に供し、マグネシウム合金板材を製造した。ロール直径は、１５２ｍｍであり、ロール温度は、８０℃とした。ロールと試料の潤滑剤として、エステル系熱間圧延用潤滑剤を用いた。 The sample temperature at the time of rolling was set to 350 ° C. to 450 ° C., the rolling speed was set to 5 m / min, the rolling reduction per pass was set to 15 to 20%, and a sample having a thickness of 5 mm was rolled to 1 mm. Finally, the rolled material was subjected to a heat treatment at 350 ° C. for 90 minutes to produce a magnesium alloy sheet. The roll diameter was 152 mm and the roll temperature was 80 ° C. An ester-based hot rolling lubricant was used as a lubricant for the roll and the sample.
比較材として、商用マグネシウム合金（ＡＺ３１Ｂ：Ｍｇ−３ｍａｓｓ％Ａｌ−１ｍａｓｓ％Ｚｎ−０．５ｍａｓｓ％Ｍｎ）の圧延材を作製した。市販の押出し材より、６０ｍｍ×５０ｍｍ×５ｍｍの試験片を切り出して、圧延を行った。圧延条件は、他の試験片と同じとした。 As a comparative material, a rolled material of a commercial magnesium alloy (AZ31B: Mg-3 mass% Al-1 mass% Zn-0.5 mass% Mn) was produced. A test piece of 60 mm × 50 mm × 5 mm was cut out from a commercially available extruded material and rolled. The rolling conditions were the same as other test pieces.
（２）Ｃａを含むマグネシウム合金板材の製造
高周波炉を用いて、純マグネシウムを溶解後、所定量のＣａ、Ｚｎ、Ａｌ、Ｍｎ、Ｚｒを添加することにより、Ｍｇ合金を作製した。後記する表３に、Ｍｇ合金材料の組成を示す。上記Ｍｇ合金（５０×３０×５０ｍｍ３）を、熱間押出し（押出し温度６７３Ｋ、押出し速度３ｍｍ／ｍｉｎ、押出し比６）に供し、押出し板材（断面積：５０×５ｍｍ２）を作製した。
(2) Manufacture of Magnesium Alloy Plate Material Containing Ca After melting pure magnesium using a high-frequency furnace, a predetermined amount of Ca, Zn, Al, Mn, and Zr was added to prepare an Mg alloy. Table 3 described later shows the composition of the Mg alloy material. The Mg alloy (50 × 30 × 50 mm 3 ) was subjected to hot extrusion (extrusion temperature 673K, extrusion speed 3 mm / min, extrusion ratio 6) to produce an extruded plate material (cross-sectional area: 50 × 5 mm 2 ).
押出し板材より、６０ｍｍ×５０ｍｍ×５ｍｍの試験片を切出し、それらの試験片を、圧延に供した。圧延時の試料温度は、３５０℃〜４５０℃とし、圧延速度を５ｍ／ｍｉｎで、厚み５ｍｍの試料を、４ｍｍもしくは１ｍｍまで圧延した。１パス毎の圧下率を１５〜２０％に設定した。最後に、圧延材を、２５０℃もしくは３５０℃で、９０分の焼鈍に供した。ロール直径は、１５２ｍｍであり、ロール温度は、８０℃以上とした。 Test pieces of 60 mm × 50 mm × 5 mm were cut out from the extruded plate material, and these test pieces were subjected to rolling. The sample temperature at the time of rolling was 350 ° C. to 450 ° C., the rolling speed was 5 m / min, and a sample having a thickness of 5 mm was rolled to 4 mm or 1 mm. The rolling reduction per pass was set to 15 to 20%. Finally, the rolled material was subjected to annealing at 250 ° C. or 350 ° C. for 90 minutes. The roll diameter was 152 mm, and the roll temperature was 80 ° C. or higher.
（３）マグネシウム合金板材の特性評価
上記マグネシウム合金板材の成形性を評価するために、エリクセン試験を実施した。エリクセン試験は、ＪＩＳ Ｂ７７２９及びＪＩＳ Ｚ２２４７に準拠した。なお、ブランク形状は、板材形状の都合上、φ６０ｍｍ（厚み１ｍｍ）とした。成形速度は、５ｍｍ／ｍｉｎとし、しわ押さえ力は、１０ｋＮとした。潤滑剤には、グラファイトグリスを利用した。
(3) Characteristic evaluation of magnesium alloy sheet In order to evaluate the formability of the magnesium alloy sheet, an Erichsen test was performed. The Eriksen test was based on JIS B7729 and JIS Z2247. The blank shape was set to 60 mm (thickness 1 mm) for the convenience of the plate material shape. The molding speed was 5 mm / min, and the wrinkle pressing force was 10 kN. Graphite grease was used as the lubricant.
上記マグネシウム合金板材の（０００２）面集合組織を、ＸＲＤ法（シュルツの反射法）により測定し、（０００２）面のＴＤ方向への極の有無を調査した。測定に際しては、圧延材より、２０ｍｍ×２０ｍｍ×１ｍｍの板材を切り出し、厚み０．５ｍｍまで面削した上で、＃４０００のＳｉＣ研磨紙で表面研磨を実施した試料を利用した。 The (0002) plane texture of the magnesium alloy sheet was measured by the XRD method (Schulz reflection method), and the presence or absence of a pole in the TD direction of the (0002) plane was investigated. At the time of measurement, a 20 mm × 20 mm × 1 mm plate was cut out from the rolled material, chamfered to a thickness of 0.5 mm, and then subjected to surface polishing with # 4000 SiC abrasive paper.
表２に、軽希土類元素を添加したマグネシウム合金板材のエリクセン試験及び集合組織測定の結果であるエリクセン値及びＴＤ方向の極の有無について、まとめて示す。試験番号４〜７、１０〜２５、２７〜３２は、実施例、試料番号１〜３、８、９、２６は、比較例である。試料番号３〜８（比較例３、４、実施例１〜４）までは、Ｃｅ量を０．２質量％と固定し、Ｚｎ量を変化させた際の結果である。 Table 2 summarizes the Erichsen values and the presence or absence of poles in the TD direction, which are the results of the Erichsen test and the texture measurement of the magnesium alloy sheet added with light rare earth elements. Test numbers 4 to 7, 10 to 25, and 27 to 32 are examples, and sample numbers 1 to 3, 8, 9, and 26 are comparative examples. Sample numbers 3 to 8 (Comparative Examples 3 and 4 and Examples 1 to 4) are the results when the Ce amount is fixed at 0.2% by mass and the Zn amount is changed.
Ｚｎを規定値（０．１質量％〜３．０質量％）に設定し、圧延温度を４５０℃に設定すると、集合組織にＴＤ方向の極が現れ、エリクセン値は、８．０以上の値を示した。表２の結果より、Ｍｇ−Ｚｎ−Ｃｅ合金の成形性は、ＡＺ３１Ｂ（試験番号１、２：比較例１、２）と比較して、著しく優れていることが分かる。 When Zn is set to a specified value (0.1% by mass to 3.0% by mass) and the rolling temperature is set to 450 ° C., poles in the TD direction appear in the texture, and the Erichsen value is a value of 8.0 or more. showed that. From the results in Table 2, it can be seen that the formability of the Mg—Zn—Ce alloy is remarkably superior to that of AZ31B (Test Nos. 1 and 2: Comparative Examples 1 and 2).
表２中の試験番号６、９（実施例３、比較例５）は、Ｚｎを１．５質量％とし、Ｃｅを０．２質量％とした合金を、４５０℃又は３９０℃で圧延した試料のエリクセン試験結果である。Ｍｇ−Ｚｎ−Ｃｅ合金に関しては、圧延温度を４５０℃に設定すると、（０００２）面集合組織にＴＤ方向の極が現れ、エリクセン値８．０以上の成形性が発現した。 Test Nos. 6 and 9 (Example 3 and Comparative Example 5) in Table 2 are samples obtained by rolling an alloy containing Zn at 1.5% by mass and Ce at 0.2% by mass at 450 ° C. or 390 ° C. It is an Eriksen test result. As for the Mg—Zn—Ce alloy, when the rolling temperature was set to 450 ° C., poles in the TD direction appeared in the (0002) plane texture, and formability with an Erichsen value of 8.0 or more was exhibited.
表２中の試験番号１０（実施例５）は、Ｚｎを１．５質量％とし、Ｃｅを０．５質量％とした合金を、４５０℃で圧延した試料のエリクセン試験結果である。Ｃｅ添加量を規定量内で変化させても、エリクセン値８．０以上の成形性が発現した。 Test number 10 (Example 5) in Table 2 is an Erichsen test result of a sample obtained by rolling an alloy containing Zn at 1.5% by mass and Ce at 0.5% by mass at 450 ° C. Even when the Ce addition amount was changed within the specified amount, moldability with an Erichsen value of 8.0 or more was developed.
表２中の試験番号１１、１２（実施例６、７）は、Ｍｇ−１．５質量％Ｚｎ−０．２質量％Ｃｅに、０．１質量％Ｍｎもしくは０．３質量％Ｚｒを添加した板材のエリクセン試験結果である。Ｍｎ及びＺｒを添加しても、集合組織は、改質され、高い成形性が確保されることが分かる。 Test Nos. 11 and 12 (Examples 6 and 7) in Table 2 add 0.1% by mass Mn or 0.3% by mass Zr to Mg-1.5% by mass Zn-0.2% by mass Ce. It is the Eriksen test result of the finished board material. It can be seen that even when Mn and Zr are added, the texture is modified and high formability is secured.
表２中の試験番号１３〜１６（実施例８〜１１）は、Ｚｎを１．５質量％添加し、Ｙを０．２〜０．４質量％添加した合金を、試料温度３５０℃〜４５０℃で圧延した試料のエリクセン試験結果である。ＣｅをＹに代替しても、また、いずれの圧延温度においても、集合組織は、改質され、板材は、８．０以上のエリクセン値を示すことが分かる。 Test numbers 13 to 16 (Examples 8 to 11) in Table 2 are obtained by adding 1.5 mass% of Zn and adding 0.2 to 0.4 mass% of Y to the sample temperature of 350 ° C to 450 ° C. It is an Eriksen test result of the sample rolled at ° C. It can be seen that even when Ce is replaced with Y, and at any rolling temperature, the texture is modified and the plate shows an Erichsen value of 8.0 or more.
表２中の試験番号１７〜１９（実施例１２〜１４）は、Ｚｎを１．５質量％添加し、Ｓｃを０．１〜０．３質量％添加した合金を、試料温度３９０℃で圧延した試料のエリクセン試験結果である。ＹをＳｃに代替しても、集合組織は、改質され、板材は、８．０以上のエリクセン値を示すことが分かる。 Test numbers 17 to 19 (Examples 12 to 14) in Table 2 are obtained by rolling an alloy containing 1.5 mass% of Zn and 0.1 to 0.3 mass% of Sc at a sample temperature of 390 ° C. It is the result of the Eriksen test of the sample. It can be seen that even if Y is replaced with Sc, the texture is modified and the plate material exhibits an Erichsen value of 8.0 or more.
表２中の試験番号２０、２１（実施例１５、１６）は、Ｚｎを１．５質量％添加し、Ｙ又はＳｃを０．２質量％添加し、Ｃｅを０．２質量％添加した合金を、試料温度３９０℃で圧延した試料のエリクセン試験結果である。ＣｅとＹ、又はＣｅとＳｃを合わせて添加しても、集合組織は、改質され、板材は、８．０以上のエリクセン値を示すことが分かる。 Test Nos. 20 and 21 (Examples 15 and 16) in Table 2 are alloys in which Zn is added by 1.5% by mass, Y or Sc is added by 0.2% by mass, and Ce is added by 0.2% by mass. Is an Erichsen test result of a sample rolled at a sample temperature of 390 ° C. It can be seen that even when Ce and Y or Ce and Sc are added together, the texture is modified, and the plate shows an Erichsen value of 8.0 or more.
表２中の試験番号２２〜２５（実施例１７〜２０）は、Ｚｎを１．５質量％とし、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍを０．２質量％添加した合金を、試料温度４５０℃圧延した試料のエリクセン試験結果である。すべての試料のエリクセン値は、８．０以上の値を示すことが分かる。 Test numbers 22 to 25 (Examples 17 to 20) in Table 2 are obtained by rolling an alloy containing Zn by 1.5 mass% and adding La, Pr, Nd, and Sm by 0.2 mass% with a sample temperature of 450 ° C. It is the result of the Eriksen test of the sample. It can be seen that the Erichsen values of all the samples show values of 8.0 or more.
表２中の試験番号２６〜２９（実施例２１〜２３、比較例６）は、Ｚｎを１．５質量％とし、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍを０．２質量％添加した合金を、試料温度３９０℃圧延した試料のエリクセン試験結果である。Ｐｒ、Ｎｄ、Ｓｍを添加した試料は、エリクセン値８．０以上の値を示す。一方、Ｌａを添加した試料のエリクセン値は、８．０未満である。 Test numbers 26 to 29 (Examples 21 to 23, Comparative Example 6) in Table 2 are samples of alloys in which Zn is 1.5% by mass and La, Pr, Nd, and Sm are added by 0.2% by mass. It is the Eriksen test result of the sample rolled at the temperature of 390 degreeC. The sample to which Pr, Nd, and Sm are added shows an Erichsen value of 8.0 or more. On the other hand, the Erichsen value of the sample to which La is added is less than 8.0.
表２中の試験番号３０〜３２（実施例２４〜２６）は、Ｚｎを１．０〜１．５質量％とし、Ｍｍを０．２〜０．５質量％添加した合金のエリクセン試験結果である。軽希土類元素の混合物を利用しても、エリクセン値８．０以上の成形性を示す。 Test numbers 30 to 32 (Examples 24 to 26) in Table 2 are Erichsen test results of alloys in which Zn is set to 1.0 to 1.5 mass% and Mm is added to 0.2 to 0.5 mass%. is there. Even if a mixture of light rare earth elements is used, the moldability with an Erichsen value of 8.0 or more is exhibited.
表３に、Ｃａを添加したマグネシウム合金板材のエリクセン試験及びＴＤ方向の極について、まとめて示す。試料番号３３，４７〜５３は、比較例、試料番号３４〜４６は、実施例である。試料番号３３〜試料番号３６までは、Ｚｎ量を１．５質量％と固定し、Ｃａ量を変化させ、試料温度４５０℃で１ｍｍまで圧延し、３５０℃（９０分）で熱処理に供した際の結果である。 Table 3 summarizes the Erichsen test and the TD-direction pole of the magnesium alloy sheet added with Ca. Sample numbers 33 and 47 to 53 are comparative examples, and sample numbers 34 to 46 are examples. For Sample No. 33 to Sample No. 36, when the Zn content was fixed at 1.5 mass%, the Ca content was changed, the sample temperature was rolled to 1 mm at 450 ° C., and subjected to heat treatment at 350 ° C. (90 minutes) Is the result of
Ｃａ量を、適正な値に設定すると、集合組織にＴＤ方向の極が現れ、エリクセン値は、８．０以上の値を示した。表３の結果より、Ｍｇ−Ｚｎ−Ｃａ系合金の成形性は、Ｍｇ−Ｚｎ系合金（試料番号３３）と比較して、著しく優れていることが分かる。 When the Ca content was set to an appropriate value, a pole in the TD direction appeared in the texture, and the Erichsen value was 8.0 or more. From the results in Table 3, it can be seen that the formability of the Mg—Zn—Ca alloy is significantly superior to that of the Mg—Zn alloy (Sample No. 33).
表３中の試験番号３５、３７、３８は、Ｃａ量を０．０８質量％とし、Ｚｎ量を変化させ、試料温度４５０℃で１ｍｍまで圧延し、３５０℃（９０分）で熱処理に供した際の結果である。Ｚｎを既定値に設定することにより、集合組織にＴＤ方向の極が現れ、エリクセン値は、８．０以上の値を示した。 Test Nos. 35, 37, and 38 in Table 3 have a Ca content of 0.08% by mass, a Zn content is changed, rolled to 1 mm at a sample temperature of 450 ° C., and subjected to heat treatment at 350 ° C. (90 minutes). Result. By setting Zn to a predetermined value, poles in the TD direction appeared in the texture, and the Erichsen value was 8.0 or more.
表３中の試験番号３９〜４２は、Ｃａ量を０．０８質量％、Ｚｎ量を１．５質量％とし、Ｍｎ、Ｚｒ、Ａｌを添加した合金を、試料温度４５０℃で１ｍｍまで圧延し、３５０℃（９０分）で熱処理に供した際の結果である。Ｚｒ、Ｍｎ、Ａｌを添加しても、集合組織にＴＤ方向の極が現れ、エリクセン値は、８．０以上の値を示した。 Test Nos. 39 to 42 in Table 3 are made by rolling an alloy containing 0.08 mass% Ca, 1.5 mass% Zn and adding Mn, Zr, and Al to a sample temperature of 450 ° C. to 1 mm. It is the result at the time of using for heat processing at 350 degreeC (90 minutes). Even when Zr, Mn, and Al were added, poles in the TD direction appeared in the texture, and the Erichsen value was 8.0 or more.
表３中の試験番号４３〜４６は、Ｚｎ量を１．５質量％とし、Ｃａ量を０．０４質量％〜０．１２質量％とし、試料温度３５０℃もしくは３９０℃で１ｍｍまで圧延し、３５０℃（９０分）で熱処理に供した際の結果である。マグネシウム合金の組成を既定値に設定すると、圧延温度にかかわらず、集合組織にＴＤ方向の極が現れ、エリクセン値は８．０以上の値を示した。 Test Nos. 43 to 46 in Table 3 have a Zn amount of 1.5 mass%, a Ca amount of 0.04 mass% to 0.12 mass%, and rolled to 1 mm at a sample temperature of 350 ° C. or 390 ° C., It is a result at the time of using for heat processing at 350 degreeC (90 minutes). When the composition of the magnesium alloy was set to a predetermined value, a pole in the TD direction appeared in the texture regardless of the rolling temperature, and the Erichsen value was 8.0 or more.
表３中の試験番号４７、４８は、Ｚｎ量を１．５質量％とし、Ｃａ量を０．０８質量％とし、試料温度３５０℃もしくは４５０℃で４ｍｍまで圧延し、３５０℃（９０分）で熱処理に供した際の結果である。規定された値よりも低い圧下率の圧延を行うと、熱処理を行っても、集合組織にＴＤ方向の極は現れない。 Test Nos. 47 and 48 in Table 3 have a Zn content of 1.5% by mass, a Ca content of 0.08% by mass, rolled to 4 mm at a sample temperature of 350 ° C. or 450 ° C., and 350 ° C. (90 minutes). It is the result at the time of using for heat processing. When rolling at a reduction rate lower than the specified value, no pole in the TD direction appears in the texture even when heat treatment is performed.
表３中の試験番号４９〜５３は、Ｚｎ量を１．５質量％とし、Ｃａ量を０．０８質量％とし、試料温度３５０℃〜４５０℃で１ｍｍまで圧延した試料の結果である。熱処理を行わない試料（試験番号５０、５２）の集合組織には、ＴＤ方向の極が現れなかった。 Test numbers 49 to 53 in Table 3 are the results of samples rolled to 1 mm at a sample temperature of 350 ° C. to 450 ° C. with a Zn content of 1.5 mass% and a Ca content of 0.08 mass%. No pole in the TD direction appeared in the texture of the samples not subjected to heat treatment (test numbers 50 and 52).
また、２５０℃（９０分）の熱処理に供した試料（試験番号５１、５３）の集合組織にも、ＴＤ方向の極は現れず、エリクセン値は、８．０未満である。すなわち、マグネシウム合金の組成を既定値に設定しても、適当な条件で熱処理を行わないと、集合組織は、改質されず、アルミニウム合金並の成形性が発現しないことが示された。 Also, no pole in the TD direction appears in the texture of the samples subjected to heat treatment at 250 ° C. (90 minutes) (test numbers 51 and 53), and the Erichsen value is less than 8.0. That is, even when the composition of the magnesium alloy is set to a predetermined value, the texture is not modified and the formability equivalent to that of the aluminum alloy is not exhibited unless heat treatment is performed under appropriate conditions.
図１に、実施例で利用したＭｇ−１．５質量％−０．２質量％Ｃｅ合金圧延材の（０００２）面集合組織を示す。これは、所定の試料温度で、厚さ５ｍｍから１ｍｍまで圧延を実施し、更に、３５０℃で９０分の焼鈍に供した試料の集合組織を表すものである。 FIG. 1 shows the (0002) plane texture of the Mg-1.5 mass% -0.2 mass% Ce alloy rolled material used in the examples. This represents the texture of a sample that was rolled from a thickness of 5 mm to 1 mm at a predetermined sample temperature and subjected to annealing at 350 ° C. for 90 minutes.
図中、（ａ）は、試料温度３９０℃で圧延を実施した試料の焼鈍前の集合組織を表し、（ｂ）は、試料温度３９０℃で圧延を実施した試料の焼鈍後の集合組織を表し、（ｃ）は、試料温度４５０℃で圧延を実施した試料の焼鈍前の集合組織を表し、（ｄ）は、試料温度４５０℃で圧延を実施した試料の焼鈍後の集合組織を表す。なお、（ｂ）は、試験番号９の試料の集合組織を示し、（ｄ）は、試験番号６の試料の集合組織を示す。 In the figure, (a) represents the texture before annealing of the sample rolled at the sample temperature of 390 ° C., and (b) represents the texture after annealing of the sample rolled at the sample temperature of 390 ° C. (C) represents the texture before annealing of the sample rolled at the sample temperature of 450 ° C., and (d) represents the texture after annealing of the sample rolled at the sample temperature of 450 ° C. (B) shows the texture of the sample of test number 9, and (d) shows the texture of the sample of test number 6.
図２に、実施例で利用した、異なる圧下率で圧延を行った、Ｍｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の、（０００２）面集合組織を示す。これは、試料温度３５０℃又は４５０℃で、厚さ５ｍｍから４ｍｍまで、もしくは厚さ５ｍｍから１ｍｍまで圧延を実施し、更に、３５０℃で９０分の焼鈍に供した試料の集合組織を表すものである。 FIG. 2 shows the (0002) plane texture of the Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material, which was used in the examples and rolled at different rolling reductions. This represents the texture of a sample subjected to rolling at a sample temperature of 350 ° C. or 450 ° C. from a thickness of 5 mm to 4 mm, or from 5 mm to 1 mm, and subjected to annealing at 350 ° C. for 90 minutes. It is.
図中、（ａ）は、３５０℃で４ｍｍまで圧延した試料の集合組織を（試験番号４７）、（ｂ）は、３５０℃で１ｍｍまで圧延した試料の集合組織を（試験番号４３）、（ｃ）は、４５０℃で４ｍｍまで圧延した試料の集合組織を（試験番号４８）、（ｄ）は、４５０℃で１ｍｍまで圧延した試料の集合組織を示す（試験番号３５）。 In the figure, (a) shows the texture of the sample rolled to 350 mm at 4 ° C. (test number 47), (b) shows the texture of the sample rolled to 350 mm at 1 mm (test number 43), ( c) shows the texture of the sample rolled to 4 mm at 450 ° C. (test number 48), and (d) shows the texture of the sample rolled to 1 mm at 450 ° C. (test number 35).
図３に、実施例で利用したＭｇ−１．５質量％Ｚｎ−０．０８質量％Ｃａ合金圧延材の熱処理前後の、（０００２）面集合組織を示す。これは、試料温度３９０℃又は４５０℃で、厚さ５ｍｍから１ｍｍまで圧延を実施し、更に、一部の試料について、２５０℃又は３５０℃で９０分の焼鈍に供した試料の集合組織を表すものである。 FIG. 3 shows the (0002) plane texture before and after heat treatment of the Mg-1.5 mass% Zn-0.08 mass% Ca alloy rolled material used in the examples. This represents the texture of a sample that was rolled at a sample temperature of 390 ° C. or 450 ° C. from a thickness of 5 mm to 1 mm, and subjected to annealing at 250 ° C. or 350 ° C. for 90 minutes for some samples. Is.
図中、（ａ）は、３９０℃で圧延した熱処理前の試料の集合組織を（試験番号５０）、（ｂ）は、３９０℃で圧延した試料を２５０℃（９０分）の熱処理に供した試料の集合組織を（試験番号５１）、（ｃ）は、３９０℃で圧延した試料を３５０℃（９０分）の熱処理に供した試料の集合組織を（試験番号４５）示す。 In the figure, (a) shows the texture of the sample before heat treatment rolled at 390 ° C. (Test No. 50), and (b) shows that the sample rolled at 390 ° C. was subjected to heat treatment at 250 ° C. (90 minutes). The sample texture (Test No. 51) and (c) show the sample texture (Test No. 45) obtained by subjecting the sample rolled at 390 ° C. to heat treatment at 350 ° C. (90 minutes).
更に、（ｄ）は、４５０℃で圧延した熱処理前の試料の集合組織を（試験番号５２）、（ｅ）は、４５０℃で圧延した試料を２５０℃（９０分）の熱処理に供した試料の集合組織を（試験番号５３）、（ｆ）は、４５０℃で圧延した試料を３５０℃（９０分）の熱処理に供した試料の集合組織を（試験番号３５）、示す。 Further, (d) shows the texture of the sample before heat treatment rolled at 450 ° C. (Test No. 52), and (e) shows the sample subjected to heat treatment at 250 ° C. (90 minutes) after being rolled at 450 ° C. And (f) shows the texture of a sample subjected to a heat treatment at 350 ° C. (90 minutes) (test number 35).
以上詳述したように、本発明は、易成形性マグネシウム合金板材及びその製造方法に係わるものであり、マグネシウムに特定量の軽希土類元素類（Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ）の１種以上、Ｚｎ、及び必要によりＭｎ、Ｚｒを添加した合金を、熱間・温間圧延に供し、更に、適当な熱処理に供することにより、Ｌｉを利用せずに、易成形性マグネシウム合金板材を作製することができる。 As described above in detail, the present invention relates to an easily moldable magnesium alloy sheet and a method for producing the same, and a specific amount of light rare earth elements (Y, Sc, La, Ce, Pr, Nd, Sm) in magnesium. 1), an alloy to which Zn, and optionally Mn and Zr are added, are subjected to hot and warm rolling, and further subjected to an appropriate heat treatment, so that easily formable magnesium without using Li. An alloy sheet can be produced.
また、本発明は、マグネシウムに特定量のＣａ、Ｚｎ、及び必要によりＡｌ、Ｍｎ、Ｚｒを添加した合金を、熱間・温間圧延に供し、更に、適当な熱処理に供することにより、Ｌｉを利用せずに、易成形性マグネシウム合金板材を作製することができる。作製されたマグネシウム合金板材の（０００２）面集合組織には、板幅方向に（０００２）面の極が現れ、集合組織の改質により、常温（３０℃）で、アルミニウム合金に準ずる、もしくは匹敵する優れた成形性が発現する。 In addition, the present invention provides an alloy obtained by adding a specific amount of Ca, Zn, and, if necessary, Al, Mn, and Zr to hot / warm rolling, and further subjecting to an appropriate heat treatment, so that Li can be obtained. An easily formable magnesium alloy sheet can be produced without using it. In the (0002) plane texture of the produced magnesium alloy sheet material, (0002) plane poles appear in the width direction of the sheet, and due to the modification of the texture, it is equivalent to or comparable to an aluminum alloy at room temperature (30 ° C.). Excellent moldability is exhibited.
本発明は、デジタルカメラ、ノートパソコン、ＰＤＡ等、主に家電製品のプレス成形体を中心として積極的に適用することが可能な易成形性マグネシウム合金板材、そのプレス成形体及び筐体等の部材を提供するものとして有用である。 The present invention relates to a readily formable magnesium alloy sheet material that can be actively applied mainly to press-formed bodies of home appliances, such as digital cameras, notebook computers, PDAs, etc., and members such as press-formed bodies and cases It is useful as a thing to provide.
Claims (29)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008292848A JP5467294B2 (en) | 2008-06-05 | 2008-11-14 | Easy-formable magnesium alloy sheet and method for producing the same |
| PCT/JP2009/002536 WO2009147861A1 (en) | 2008-06-05 | 2009-06-04 | Easily formable magnesium alloy sheet and process for production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008148538 | 2008-06-05 | ||
| JP2008148538 | 2008-06-05 | ||
| JP2008292848A JP5467294B2 (en) | 2008-06-05 | 2008-11-14 | Easy-formable magnesium alloy sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010013725A true JP2010013725A (en) | 2010-01-21 |
| JP5467294B2 JP5467294B2 (en) | 2014-04-09 |
Family
ID=41397941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008292848A Active JP5467294B2 (en) | 2008-06-05 | 2008-11-14 | Easy-formable magnesium alloy sheet and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5467294B2 (en) |
| WO (1) | WO2009147861A1 (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011179075A (en) * | 2010-03-01 | 2011-09-15 | National Institute Of Advanced Industrial Science & Technology | Magnesium alloy sheet material having improved cold-formability and in-plane anisotropy, and method for manufacturing the same |
| JP2011195868A (en) * | 2010-03-18 | 2011-10-06 | National Institute For Materials Science | Magnesium alloy |
| WO2012077758A1 (en) * | 2010-12-08 | 2012-06-14 | 独立行政法人産業技術総合研究所 | Method for producing magnesium alloy rolled stock, magnesium alloy rolled stock, and press-molded body |
| JP2012122102A (en) * | 2010-12-08 | 2012-06-28 | National Institute Of Advanced Industrial Science & Technology | Magnesium alloy sheet material improved in cold formability and strength, and method for producing the same |
| JP2013129914A (en) * | 2011-11-22 | 2013-07-04 | National Institute Of Advanced Industrial Science & Technology | Method for producing magnesium alloy sheet material, magnesium alloy sheet material, and press molding using the same |
| JP2013533375A (en) * | 2010-05-24 | 2013-08-22 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション | Magnesium alloy for extension applications |
| WO2013180122A1 (en) | 2012-05-31 | 2013-12-05 | 独立行政法人物質・材料研究機構 | Magnesium alloy, magnesium alloy member and method for manufacturing same, and method for using magnesium alloy |
| JP2014534338A (en) * | 2011-10-06 | 2014-12-18 | ユニバーシティ オブ ピッツバーグ オブ ザ コモンウェルス システム オブ ハイヤー エデュケーションＵｎｉｖｅｒｓｉｔｙ Ｏｆ Ｐｉｔｔｓｂｕｒｇｈ Ｏｆ Ｔｈｅ Ｃｏｍｍｏｎｗｅａｌｔｈ Ｓｙｓｔｅｍ Ｏｆ Ｈｉｇｈｅｒ Ｅｄｕｃａｔｉｏｎ | Biodegradable metal alloy |
| CN104284992A (en) * | 2012-06-26 | 2015-01-14 | 百多力股份公司 | Magnesium-zinc-calcium alloy, method for production thereof, and use thereof |
| CN104419854A (en) * | 2013-09-02 | 2015-03-18 | 丰田自动车株式会社 | Pseudoelastic magnesium alloy, pseudoelastic magnesium alloy component, and production method thereof |
| JP2016516126A (en) * | 2013-05-07 | 2016-06-02 | 宝山鋼鉄股▲分▼有限公司 | Inexpensive fine-grain weak-structure magnesium alloy sheet and method for producing the same |
| CN106521278A (en) * | 2016-12-29 | 2017-03-22 | 湘潭大学 | High-strength magnesium-zinc-manganese-yttrium-cerium magnesium alloy and preparation method thereof |
| EP2644728A4 (en) * | 2010-11-23 | 2017-05-17 | Postech Academy-industry Foundation | Magnesium alloy sheet having superior formability at room temperature, and method for manufacturing same |
| CN108425054A (en) * | 2018-04-13 | 2018-08-21 | 东北大学 | The high energy-absorbing magnesium alloy of high-ductility and can depth clod wash tubing preparation facilities and method |
| CN108431261A (en) * | 2015-12-28 | 2018-08-21 | 韩国机械研究院 | Magnesium alloy and its manufacturing method with excellent mechanical performance and corrosion resistance |
| WO2018159394A1 (en) | 2017-02-28 | 2018-09-07 | 国立研究開発法人物質・材料研究機構 | Magnesium alloy and method for manufacturing magnesium alloy |
| CN110267691A (en) * | 2016-10-31 | 2019-09-20 | 尤安艾股份公司 | Biodegradable magnesium alloy and its manufacturing method |
| JP2019535893A (en) * | 2016-10-21 | 2019-12-12 | ポスコＰｏｓｃｏ | Highly formed magnesium alloy sheet and method for producing the same |
| JP2020503453A (en) * | 2016-12-23 | 2020-01-30 | ポスコＰｏｓｃｏ | Magnesium alloy plate and method of manufacturing the same |
| WO2021131205A1 (en) * | 2019-12-23 | 2021-07-01 | 住友電気工業株式会社 | Magnesium alloy plate and magnesium alloy coil material |
| CN113073275A (en) * | 2021-03-22 | 2021-07-06 | 湖南工程学院 | Preparation method of magnesium alloy plate with four-peak non-basal texture characteristics |
| WO2021215241A1 (en) | 2020-04-21 | 2021-10-28 | 国立研究開発法人産業技術総合研究所 | Magnesium alloy, magnesium alloy plate, magnesium alloy rod, methods for producing these, and magnesium alloy member |
| US11160674B2 (en) | 2017-01-30 | 2021-11-02 | Japan Medical Device Technology Co., Ltd. | High performance bioabsorbable stent |
| US11248282B2 (en) * | 2017-01-10 | 2022-02-15 | Fuji Light Metal Co., Ltd. | Magnesium alloy |
| US11685975B2 (en) | 2018-07-09 | 2023-06-27 | Japan Medical Device Technology Co., Ltd. | Magnesium alloy |
| US11739400B2 (en) | 2018-02-21 | 2023-08-29 | National Institute For Materials Science | Magnesium alloy and method for manufacturing the same |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2426228B1 (en) * | 2010-09-03 | 2015-05-20 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium sheet semi-finished products with improved cold reforming characteristics |
| CN102632100A (en) * | 2012-04-25 | 2012-08-15 | 中南大学 | Method for processing high-extensibility magnesium alloy slat |
| CA2869103C (en) | 2012-06-26 | 2023-05-02 | Biotronik Ag | Magnesium-zinc-calcium alloy, method for production thereof and use thereof |
| SG11201406021PA (en) | 2012-06-26 | 2014-10-30 | Biotronik Ag | Magnesium-aluminum-zinc alloy, method for the production thereof and use thereof |
| RU2017138378A (en) | 2012-06-26 | 2019-02-11 | Биотроник Аг | MAGNESIUM ALLOY, METHOD OF ITS PRODUCTION AND USE |
| US9469889B2 (en) | 2012-08-31 | 2016-10-18 | DePuy Synthes Products, Inc. | Ultrapure magnesium alloy with adjustable degradation rate |
| US9593397B2 (en) | 2013-03-14 | 2017-03-14 | DePuy Synthes Products, Inc. | Magnesium alloy with adjustable degradation rate |
| BR112015022632B1 (en) | 2013-03-14 | 2020-01-07 | DePuy Synthes Products, Inc. | MAGNESIUM ALLOY COMPOSITION, IMPLANT, AND COMPOSITION PRODUCTION METHOD |
| CN103556092B (en) * | 2013-11-15 | 2015-12-09 | 重庆大学 | A kind of method improving Mg alloy formed performance |
| CN104131204B (en) * | 2014-08-19 | 2017-01-25 | 中国科学院长春应用化学研究所 | Magnesium alloy, magnesium alloy composite material and preparation method of composite material |
| CN104498796A (en) * | 2014-12-15 | 2015-04-08 | 苏州昊卓新材料有限公司 | Preparation method of Mg alloy |
| CN105886866A (en) * | 2016-06-22 | 2016-08-24 | 重庆大学 | High-formability magnesium alloy |
| CN106222507B (en) * | 2016-09-06 | 2018-05-01 | 重庆大学 | A kind of low cost high-damping high intensity Mg-Zn-Ce alloys and preparation method thereof |
| KR102045063B1 (en) * | 2017-08-03 | 2019-12-02 | 주식회사 포스코 | Magnesium alloy sheet and method for manufacturing the same |
| CN107698278B (en) * | 2017-10-31 | 2021-01-05 | 湖北天宝光电科技有限公司 | Annealing method of ceramic rear cover |
| CN115181879A (en) * | 2019-01-30 | 2022-10-14 | 四川镁合医疗器械有限责任公司 | Degradable magnesium alloy in-situ composite anastomosis nail and preparation method thereof |
| EP3741880B1 (en) * | 2019-05-20 | 2023-06-28 | Volkswagen AG | Sheet metal product with high bendability and manufacturing thereof |
| CN110117743B (en) * | 2019-05-24 | 2020-08-11 | 珠海中科先进技术研究院有限公司 | Corrosion-resistant high-strength toughness magnesium alloy pipe and preparation process thereof |
| CN113278857B (en) * | 2021-04-02 | 2022-06-28 | 中国兵器科学研究院宁波分院 | High-toughness magnesium alloy and preparation method thereof |
| CN113444945B (en) * | 2021-07-02 | 2022-04-26 | 云南大学 | High-plasticity high-formability magnesium alloy plate with annular divergent texture and preparation method thereof |
| CN115044813A (en) * | 2022-04-29 | 2022-09-13 | 北京工业大学 | Low-cost high-strength magnesium alloy material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293944A (en) * | 1993-04-06 | 1994-10-21 | Nippon Steel Corp | Production of magnesium alloy sheet excellent in press formability |
| JP2003126943A (en) * | 2001-10-19 | 2003-05-08 | Nippon Kinzoku Co Ltd | Manufacturing method of magnesium alloy slab for hot- rolling and method for hot-rolling magnesium alloy |
| JP2005298885A (en) * | 2004-04-09 | 2005-10-27 | Nippon Kinzoku Co Ltd | Magnesium or magnesium alloy sheet having excellent plastic workability and its production method |
-
2008
- 2008-11-14 JP JP2008292848A patent/JP5467294B2/en active Active
-
2009
- 2009-06-04 WO PCT/JP2009/002536 patent/WO2009147861A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293944A (en) * | 1993-04-06 | 1994-10-21 | Nippon Steel Corp | Production of magnesium alloy sheet excellent in press formability |
| JP2003126943A (en) * | 2001-10-19 | 2003-05-08 | Nippon Kinzoku Co Ltd | Manufacturing method of magnesium alloy slab for hot- rolling and method for hot-rolling magnesium alloy |
| JP2005298885A (en) * | 2004-04-09 | 2005-10-27 | Nippon Kinzoku Co Ltd | Magnesium or magnesium alloy sheet having excellent plastic workability and its production method |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011179075A (en) * | 2010-03-01 | 2011-09-15 | National Institute Of Advanced Industrial Science & Technology | Magnesium alloy sheet material having improved cold-formability and in-plane anisotropy, and method for manufacturing the same |
| JP2011195868A (en) * | 2010-03-18 | 2011-10-06 | National Institute For Materials Science | Magnesium alloy |
| US9945011B2 (en) | 2010-05-24 | 2018-04-17 | Commonwealth Scientific And Industrial Research Organisation | Magnesium-based alloy for wrought applications |
| JP2013533375A (en) * | 2010-05-24 | 2013-08-22 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション | Magnesium alloy for extension applications |
| EP2644728A4 (en) * | 2010-11-23 | 2017-05-17 | Postech Academy-industry Foundation | Magnesium alloy sheet having superior formability at room temperature, and method for manufacturing same |
| WO2012077758A1 (en) * | 2010-12-08 | 2012-06-14 | 独立行政法人産業技術総合研究所 | Method for producing magnesium alloy rolled stock, magnesium alloy rolled stock, and press-molded body |
| JP2012122102A (en) * | 2010-12-08 | 2012-06-28 | National Institute Of Advanced Industrial Science & Technology | Magnesium alloy sheet material improved in cold formability and strength, and method for producing the same |
| JP2014534338A (en) * | 2011-10-06 | 2014-12-18 | ユニバーシティ オブ ピッツバーグ オブ ザ コモンウェルス システム オブ ハイヤー エデュケーションＵｎｉｖｅｒｓｉｔｙ Ｏｆ Ｐｉｔｔｓｂｕｒｇｈ Ｏｆ Ｔｈｅ Ｃｏｍｍｏｎｗｅａｌｔｈ Ｓｙｓｔｅｍ Ｏｆ Ｈｉｇｈｅｒ Ｅｄｕｃａｔｉｏｎ | Biodegradable metal alloy |
| JP2018021251A (en) * | 2011-10-06 | 2018-02-08 | ユニバーシティ オブ ピッツバーグ オブ ザ コモンウェルス システム オブ ハイヤー エデュケーションＵｎｉｖｅｒｓｉｔｙ Ｏｆ Ｐｉｔｔｓｂｕｒｇｈ Ｏｆ Ｔｈｅ Ｃｏｍｍｏｎｗｅａｌｔｈ Ｓｙｓｔｅｍ Ｏｆ Ｈｉｇｈｅｒ Ｅｄｕｃａｔｉｏｎ | Biodegradable metal alloys |
| JP2013129914A (en) * | 2011-11-22 | 2013-07-04 | National Institute Of Advanced Industrial Science & Technology | Method for producing magnesium alloy sheet material, magnesium alloy sheet material, and press molding using the same |
| WO2013180122A1 (en) | 2012-05-31 | 2013-12-05 | 独立行政法人物質・材料研究機構 | Magnesium alloy, magnesium alloy member and method for manufacturing same, and method for using magnesium alloy |
| JP2019137921A (en) * | 2012-06-26 | 2019-08-22 | バイオトロニック アクチェンゲゼルシャフト | Magnesium alloy, method for production thereof, and use thereof |
| JP7448581B2 (en) | 2012-06-26 | 2024-03-12 | バイオトロニック アクチェンゲゼルシャフト | Magnesium alloy, its production method and its use |
| US11499214B2 (en) | 2012-06-26 | 2022-11-15 | Biotronik Ag | Magnesium-zinc-calcium alloy and method for producing implants containing the same |
| JP2022084916A (en) * | 2012-06-26 | 2022-06-07 | バイオトロニック アクチェンゲゼルシャフト | Magnesium alloy, method for production thereof, and use thereof |
| JP7053529B2 (en) | 2012-06-26 | 2022-04-12 | バイオトロニック アクチェンゲゼルシャフト | Magnesium alloy, its manufacturing method and its use |
| CN104284992A (en) * | 2012-06-26 | 2015-01-14 | 百多力股份公司 | Magnesium-zinc-calcium alloy, method for production thereof, and use thereof |
| JP2016516126A (en) * | 2013-05-07 | 2016-06-02 | 宝山鋼鉄股▲分▼有限公司 | Inexpensive fine-grain weak-structure magnesium alloy sheet and method for producing the same |
| US10000836B2 (en) | 2013-05-07 | 2018-06-19 | Baoshan Iron & Steel Co., Ltd. | Low-cost fine-grain weak-texture magnesium alloy sheet and method of manufacturing the same |
| JP2015063746A (en) * | 2013-09-02 | 2015-04-09 | トヨタ自動車株式会社 | Magnesium alloy showing anelasticity, magnesium alloy component showing anelasticity and method of producing the same |
| CN104419854A (en) * | 2013-09-02 | 2015-03-18 | 丰田自动车株式会社 | Pseudoelastic magnesium alloy, pseudoelastic magnesium alloy component, and production method thereof |
| JP2019502821A (en) * | 2015-12-28 | 2019-01-31 | コリア インスティテュート オブ マシーナリー アンド マテリアルズＫｏｒｅａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｍａｃｈｉｎｅｒｙ ＆ Ｍａｔｅｒｉａｌｓ | Magnesium alloy having excellent mechanical properties and corrosion resistance and method for producing the same |
| CN108431261A (en) * | 2015-12-28 | 2018-08-21 | 韩国机械研究院 | Magnesium alloy and its manufacturing method with excellent mechanical performance and corrosion resistance |
| US10947609B2 (en) | 2015-12-28 | 2021-03-16 | Korea Institute Of Materials Science | Magnesium alloy having excellent mechanical properties and corrosion resistance and method for manufacturing the same |
| JP2019535893A (en) * | 2016-10-21 | 2019-12-12 | ポスコＰｏｓｃｏ | Highly formed magnesium alloy sheet and method for producing the same |
| CN110267691A (en) * | 2016-10-31 | 2019-09-20 | 尤安艾股份公司 | Biodegradable magnesium alloy and its manufacturing method |
| JP2020503453A (en) * | 2016-12-23 | 2020-01-30 | ポスコＰｏｓｃｏ | Magnesium alloy plate and method of manufacturing the same |
| US11149330B2 (en) | 2016-12-23 | 2021-10-19 | Posco | Magnesium alloy plate and method for manufacturing same |
| CN106521278A (en) * | 2016-12-29 | 2017-03-22 | 湘潭大学 | High-strength magnesium-zinc-manganese-yttrium-cerium magnesium alloy and preparation method thereof |
| US11248282B2 (en) * | 2017-01-10 | 2022-02-15 | Fuji Light Metal Co., Ltd. | Magnesium alloy |
| US11160674B2 (en) | 2017-01-30 | 2021-11-02 | Japan Medical Device Technology Co., Ltd. | High performance bioabsorbable stent |
| WO2018159394A1 (en) | 2017-02-28 | 2018-09-07 | 国立研究開発法人物質・材料研究機構 | Magnesium alloy and method for manufacturing magnesium alloy |
| US11739400B2 (en) | 2018-02-21 | 2023-08-29 | National Institute For Materials Science | Magnesium alloy and method for manufacturing the same |
| CN108425054A (en) * | 2018-04-13 | 2018-08-21 | 东北大学 | The high energy-absorbing magnesium alloy of high-ductility and can depth clod wash tubing preparation facilities and method |
| CN108425054B (en) * | 2018-04-13 | 2019-10-01 | 东北大学 | The high energy-absorbing magnesium alloy of high-ductility and can depth clod wash tubing preparation facilities and method |
| US11685975B2 (en) | 2018-07-09 | 2023-06-27 | Japan Medical Device Technology Co., Ltd. | Magnesium alloy |
| WO2021131205A1 (en) * | 2019-12-23 | 2021-07-01 | 住友電気工業株式会社 | Magnesium alloy plate and magnesium alloy coil material |
| KR20220162137A (en) | 2020-04-21 | 2022-12-07 | 고쿠리츠켄큐카이하츠호진 상교기쥬츠 소고켄큐쇼 | Magnesium alloy, magnesium alloy plate, magnesium alloy rod and manufacturing method thereof, magnesium alloy member |
| WO2021215241A1 (en) | 2020-04-21 | 2021-10-28 | 国立研究開発法人産業技術総合研究所 | Magnesium alloy, magnesium alloy plate, magnesium alloy rod, methods for producing these, and magnesium alloy member |
| CN113073275A (en) * | 2021-03-22 | 2021-07-06 | 湖南工程学院 | Preparation method of magnesium alloy plate with four-peak non-basal texture characteristics |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5467294B2 (en) | 2014-04-09 |
| WO2009147861A1 (en) | 2009-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5467294B2 (en) | Easy-formable magnesium alloy sheet and method for producing the same | |
| KR100509648B1 (en) | High formability the Magnesium alloy and manufacture method of the Magnesium alloy product thereof | |
| KR100671195B1 (en) | High temperature structural Mg alloys containing misch metal | |
| JP3905115B2 (en) | High strength and high toughness magnesium alloy and method for producing the same | |
| JP5515167B2 (en) | Commercial magnesium alloy sheet with improved room temperature formability and method for producing the same | |
| JP6794264B2 (en) | Magnesium-lithium alloy, rolled materials and molded products | |
| JP4189687B2 (en) | Magnesium alloy material | |
| JP5692847B2 (en) | Magnesium alloy sheet with improved room temperature formability and strength and method for producing the same | |
| JP5565617B2 (en) | Method for producing magnesium alloy material and magnesium alloy material | |
| JP5660525B2 (en) | General-purpose magnesium alloy sheet that exhibits formability similar to that of aluminum alloy and method for producing the same | |
| JP2012214853A (en) | Magnesium alloy and method for producing the same | |
| CN113528900A (en) | Short-process high-conductivity 6-series aluminum alloy plate strip and preparation method thereof | |
| CN108315618B (en) | Preparation method of LPSO structure reinforced magnesium-lithium alloy | |
| KR20080023192A (en) | Method for making aluminum alloy sheets for forming | |
| JP5297855B2 (en) | Copper alloy sheet and manufacturing method thereof | |
| JP4599594B2 (en) | Press molded body made of magnesium alloy large cross rolled material | |
| KR20150017143A (en) | Magnesium alloy for extrusion with excellent plasticity―workability and method for producing the same | |
| JP2011179075A (en) | Magnesium alloy sheet material having improved cold-formability and in-plane anisotropy, and method for manufacturing the same | |
| JP2010053386A (en) | Magnesium alloy sheet material which is excellent in formability, and producing method therefor | |
| JP6718276B2 (en) | Method for manufacturing Al-Mg-Si alloy plate | |
| CN112281093A (en) | Preparation process of high-performance magnesium-lithium alloy thin strip | |
| US11186899B2 (en) | Magnesium-zinc-manganese-tin-yttrium alloy and method for making the same | |
| WO2009113601A1 (en) | Magnesium-lithium alloy, rolled material and molded article | |
| CN111172439A (en) | Refined grain magnesium alloy and preparation method thereof | |
| JP5412666B2 (en) | Magnesium alloy and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20111116 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130618 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130815 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131001 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131118 |
|
| 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: 20131204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131226 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5467294 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 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 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| 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 |