JP4352127B2 - High performance magnesium alloy and method for producing the same - Google Patents
High performance magnesium alloy and method for producing the same Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000011777 magnesium Substances 0.000 claims description 48
- 239000011701 zinc Substances 0.000 claims description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- 229910052727 yttrium Inorganic materials 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 25
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 17
- 229910000765 intermetallic Inorganic materials 0.000 claims description 12
- 210000001787 dendrite Anatomy 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 230000008520 organization Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 28
- 239000000956 alloy Substances 0.000 description 25
- 229910045601 alloy Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004512 die casting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007528 sand casting Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Description
本発明は、高性能マグネシウム合金及びその製造方法に関するものであり、更に詳しくは、強度特性及び剛性特性がともに優れた高性能マグネシウム合金、その製造方法及びそれを用いた部材に関するものである。本発明は、実用構造金属材料の技術分野において、その高性能化が期待されているマグネシウム合金について、従来の製品は、例えば、安定した強度、剛性及び弾性率等の点で、更なる高性能化が強く求められていることを踏まえ、その強度と弾性率を向上させることで、次世代の構造用材料として好適に使用することを可能とする、新規高性能マグネシウム合金の製造方法及びその製品を提供するものであり、例えば、自動車をはじめとする輸送機部品及び宇宙・航空機部品、電気・電子機器部品等の幅広い分野で利用することが可能な高性能マグネシウム合金を提供するものとして有用である。 The present invention relates to a high-performance magnesium alloy and a method for producing the same, and more particularly to a high-performance magnesium alloy having both excellent strength characteristics and rigidity properties, a method for producing the same, and a member using the same. The present invention relates to magnesium alloys that are expected to have high performance in the technical field of practical structural metal materials. For example, conventional products have higher performance in terms of stable strength, rigidity, elastic modulus, and the like. In light of the strong demand for a high-performance magnesium alloy, a method for producing a new high-performance magnesium alloy and its product that can be suitably used as a next-generation structural material by improving its strength and elastic modulus For example, it is useful for providing high-performance magnesium alloys that can be used in a wide range of fields such as transportation parts such as automobiles, space / aircraft parts, and electrical / electronic equipment parts. is there.
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、金属特有の優れたリサイクル性を有し、資源も豊富に存在することから、次世代の構造用材料として注目されている材料である。現在のところ、日本におけるマグネシウム製品の多くは、鋳造法により製造されている。主なマグネシウム製品としては、例えば、ステアリングホイール、シリンダーヘッド等の自動車部品及び携帯電話筐体等の家電製品部品が挙げられる。現在、マグネシウム製品に使用されているマグネシウム合金は、主にＭｇ−Ａｌ−Ｚｎ（−Ｍｎ）系合金、例えば、ＡＺ９１合金（＝Ｍｇ−９重量％Ａｌ−１重量％Ｚｎ−０．５重量％Ｍｎ）、ＡＭ６０合金（＝Ｍｇ−６重量％Ａｌ−０．５重量％Ｍｎ）である。これらの合金の鋳造技術は、完成段階にあり、製品部材のマグネシウム化を図る際は、先ず、上記合金が検討される。 Magnesium has the lowest density (= 1.7 g / cm 3 ) among practical structural metal materials, has excellent recyclability unique to metals, and has abundant resources. It is a material that is attracting attention. At present, many magnesium products in Japan are manufactured by casting. Examples of main magnesium products include automobile parts such as a steering wheel and a cylinder head, and home appliance parts such as a mobile phone casing. Currently, magnesium alloys used in magnesium products are mainly Mg—Al—Zn (—Mn) alloys such as AZ91 alloy (= Mg-9 wt% Al-1 wt% Zn-0.5 wt%). Mn), AM60 alloy (= Mg-6 wt% Al-0.5 wt% Mn). The casting technology of these alloys is in the completion stage, and when the product member is made into magnesium, the above alloys are first examined.
しかしながら、上記合金は、その室温強度（ＡＺ９１Ｅ−Ｔ６：２７５ＭＰａ、ＡＭ６０Ｂ−Ｆ：２０５ＭＰａ）が、従来のアルミニウム合金（例えば、６０６１−Ｔ６：３１５ＭＰａ）と比較して劣ること、また、３９３Ｋ以上で、強度の劣化が始まること等の欠点を抱えており、安定した強度が必要とされる自動車部品等への適用は、制限されている。また、マグネシウムは、その弾性率（約４４．３ＧＰａ）が、アルミ（７５．８ＧＰａ）、チタン（１１４ＧＰａ）、鉄（１９０ＧＰａ）と比べると低い値であり、剛性を保証する必要がある構造部材への適用が、制限されている。 However, the above-mentioned alloy has a room temperature strength (AZ91E-T6: 275 MPa, AM60B-F: 205 MPa) inferior to a conventional aluminum alloy (for example, 6061-T6: 315 MPa), and at 393 K or more, It has drawbacks such as the start of strength deterioration, and its application to automobile parts and the like that require stable strength is limited. Magnesium has a lower elastic modulus (about 44.3 GPa) than aluminum (75.8 GPa), titanium (114 GPa), and iron (190 GPa), and is a structural member that needs to ensure rigidity. Application is limited.
強度向上を目的として提案されたマグネシウム合金としては、希土類金属（イットリウム、ネオジウム、ランタン、セリウム、ミッシュメタル）を、マグネシウムに固溶させて強化を図る固溶強化型マグネシウム合金（例えば、非特許文献１参照）、シリコンやカルシウムを添加元素とし、安定な析出物を析出させる析出強化型マグネシウム合金（例えば、非特許文献２参照）が挙げられる。また、固溶強化と析出強化を同時に達成する手法も提案されている。その例として、マグネシウム合金中に、マグネシウムとイットリウム等の希土類金属及び亜鉛やカルシウムとの金属間化合物を析出させたマグネシウム合金を、急冷凝固法により作製する方法が挙げられる（例えば、特許文献１参照）。 As a magnesium alloy proposed for the purpose of improving the strength, a solid solution strengthened magnesium alloy for strengthening by dissolving a rare earth metal (yttrium, neodymium, lanthanum, cerium, misch metal) in magnesium (for example, non-patent document) 1), precipitation strengthened magnesium alloys that use silicon or calcium as an additive element to precipitate stable precipitates (for example, see Non-Patent Document 2). A method for simultaneously achieving solid solution strengthening and precipitation strengthening has also been proposed. As an example, there is a method in which a magnesium alloy in which a rare earth metal such as magnesium and yttrium and an intermetallic compound of zinc or calcium are precipitated in a magnesium alloy is prepared by a rapid solidification method (see, for example, Patent Document 1). ).
しかし、上記の手法は、いずれも、材料の常温引張り強度及び高温引張り強度（クリープ強度）の向上を目的としたものであり、材料の弾性率を向上させる手法ではない。このような状況下にあって、本発明者らは、上記従来技術に鑑みて、マグネシウム合金の弾性率を向上させて、強度特性及び剛性特性がともに優れた高性能マグネシウム合金を得ることを目標として鋭意研究を積み重ねた結果、マグネシウムに適量の亜鉛及びイットリウムを添加し、公知の鋳造法により、冷却速度として、比較的遅い冷却速度を選択して凝固させることにより、高弾性率の組織を含有する、高強度マグネシウム合金を作製することに成功した。具体的には、上記手法により、通常のマグネシウム合金の弾性率（約４４．３ＧＰａ）よりも高い値を有するマグネシウム合金を作製する手法を開発することに成功し、更に研究を重ねて、本発明を完成するに至った。本発明は、強度特性及び剛性特性がともに優れた高性能マグネシウム合金を製造する方法及びその製品を提供することを目的とするものである。 However, each of the above methods is intended to improve the normal temperature tensile strength and high temperature tensile strength (creep strength) of the material, and is not a method for improving the elastic modulus of the material. Under such circumstances, in view of the above prior art, the present inventors have aimed to improve the elastic modulus of the magnesium alloy and obtain a high-performance magnesium alloy excellent in both strength characteristics and rigidity characteristics. As a result of intensive research, we added a suitable amount of zinc and yttrium to magnesium and contained a structure with high elastic modulus by solidifying by selecting a relatively slow cooling rate as a cooling rate by a known casting method. Succeeded in producing a high-strength magnesium alloy. Specifically, by the above method, the inventors succeeded in developing a method for producing a magnesium alloy having a higher value than the elastic modulus (about 44.3 GPa) of a normal magnesium alloy. It came to complete. An object of the present invention is to provide a method for producing a high-performance magnesium alloy excellent in both strength characteristics and rigidity characteristics, and a product thereof.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）高強度と高弾性率を有する高性能マグネシウム合金であって、イットリウム（Ｙ）を５原子％から１２原子％（５原子％≦Ｙ≦１２原子％）及び亜鉛（Ｚｎ）を１原子％から１２原子％（１原子％≦Ｚｎ≦１２原子％）含有し、残部がマグネシウムと不可避の不純物からなり、組織は、デンドライト部とマトリックス部の２相であり、マグネシウムとイットリウムと亜鉛により構成される金属間化合物が析出しており、弾性率が４４．３ＧＰａより高い値を有し、ビッカース硬度が、７９〜１１６ＨＶである、弾性率と強度を向上させたマグネシウム合金である、ことを特徴とする高性能マグネシウム合金。
（２）前記（１）に記載の強度と弾性率を向上させた高性能マグネシウム合金を製造する方法であって、マグネシウムに、イットリウム（Ｙ）及び亜鉛（Ｚｎ）を、５原子％≦Ｙ≦１２原子％及び１原子％≦Ｚｎ≦１２原子％となるように配合し、凝固速度が５０Ｋ／秒未満の条件で鋳造法により溶解・凝固させることにより、マグネシウムとイットリウムと亜鉛により構成される金属間化合物を析出させることを特徴とする高性能マグネシウム合金の製造方法。
（３）前記（１）に記載の強度と弾性率を向上させた高性能マグネシウム合金からなることを特徴とする高性能マグネシウム合金部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) A high-performance magnesium alloy having high strength and high elastic modulus, Lee Ttoriumu (Y) of 12 atomic% to 5 atomic percent (5 at% ≦ Y ≦ 12 atomic%) and zinc (Zn) 1 atomic% 12 atomic% (1 atomic% ≦ Zn ≦ 12 atomic%) contained, and the balance of magnesium and inevitable impurities, organization is a two-phase dendrites portion and the matrix portion, magnesium and Lee Ttoriumu magnesium and out analysis consists intermetallic compound, the elastic modulus has a value higher than 44.3GPa, Vickers hardness is 79 -116 H V, with improved elastic modulus and strength by zinc A high-performance magnesium alloy characterized by being an alloy.
(2) A method for producing a high performance magnesium alloy with improved strength and elastic modulus as described in (1) above, wherein yttrium (Y) and zinc (Zn) are added to magnesium at 5 atomic% ≦ Y ≦. formulated as a 12 atomic% and 1 atomic% ≦ Zn ≦ 12 atomic%, by dissolving and solidified by casting under the conditions below the freezing rate is 50K / sec, composed of magnesium and Lee Ttoriumu and zinc method for producing a high magnesium alloy, which comprises causing out analysis intermetallic compound.
(3) High-performance magnesium alloy member characterized by comprising a high magnesium alloy with improved strength of the elastic modulus according to (1).
次に、本発明について、更に詳細に説明する。
本発明者らは、マグネシウム合金の強度及び弾性率を向上させる手段として、粉末冶金法、急冷凝固法及び加工熱処理を利用して作製されるＭｇ−Ｙ−Ｚｎ合金（特許文献１参照）に注目した。この合金は、Ｙを０原子％以上４．５原子％以下含有したＭｇ−Ｙ−Ｚｎ系合金であり、微結晶かつＭｇ−Ｙ、Ｍｇ−Ｚｎ系金属間化合物を有する合金である。上記組成及び手法で作製されるマグネシウム合金は、約６００ＭＰａ程度の引張り強度を発現する。これは、商用チタン合金（Ｔｉ−６Ａｌ−４Ｖ）鋳造材の強度に匹敵する。
Next, the present invention will be described in more detail.
The present inventors pay attention to a Mg—Y—Zn alloy (see Patent Document 1) produced by using a powder metallurgy method, a rapid solidification method, and a thermomechanical treatment as a means for improving the strength and elastic modulus of a magnesium alloy. did. This alloy is an Mg—Y—Zn alloy containing Y in an amount of 0 atomic% to 4.5 atomic%, and is an alloy having microcrystals and Mg—Y and Mg—Zn intermetallic compounds. The magnesium alloy produced by the above composition and method exhibits a tensile strength of about 600 MPa. This is comparable to the strength of commercial titanium alloy (Ti-6Al-4V) castings.
上記マグネシウム合金が高強度を有する理由としては、具体的に以下の項目；（１）作製された合金が、微結晶であること、（２）マグネシウムと原子半径が異なるイットリウム及び亜鉛を強制固溶させて、固溶強化が達成していること、（３）Ｍｇ−Ｙ系、Ｍｇ−Ｚｎ系金属間化合物が、合金内部に均一に析出しており、析出強化が達成していること、が挙げられる。 The reason why the magnesium alloy has high strength is specifically as follows: (1) the produced alloy is microcrystalline; (2) yttrium and zinc having a different atomic radius from magnesium are forcibly dissolved. (3) Mg—Y and Mg—Zn intermetallic compounds are uniformly deposited inside the alloy, and precipitation strengthening is achieved. Can be mentioned.
従来、Ｍｇ−Ｙ−Ｚｎ系高強度マグネシウム合金を作製するためには、結晶粒を微細にする必要があり、また、イットリウムと亜鉛を、急冷法により強制固溶させる必要があった。そのため、従来の方法は、大量生産される自動車部材等への適用は、困難とされていた。また、従来法で作製される合金の母相は、マグネシウム固溶体であるため、マグネシウム合金の剛性（弾性率）を向上させることは困難であった。そこで、本発明者らは、上記の課題を解決するために、種々検討を重ねた結果、イットリウムと亜鉛の添加量及び冷却速度を調整すること、それにより、大量生産される部材等への適用が困難とされていた急冷法に依らなくとも、高い強度を有し、高い弾性率を有する高性能マグネシウム合金を作製し得ること、を見出した。 Conventionally, in order to produce an Mg—Y—Zn-based high-strength magnesium alloy, it is necessary to make the crystal grains fine, and it is necessary to forcibly dissolve yttrium and zinc by a rapid cooling method. Therefore, it has been difficult to apply the conventional method to automobile members and the like that are mass-produced. Moreover, since the parent phase of the alloy produced by the conventional method is a magnesium solid solution, it has been difficult to improve the rigidity (elastic modulus) of the magnesium alloy. Therefore, the present inventors have made various studies in order to solve the above problems, and as a result, adjusted the addition amount of yttrium and zinc and the cooling rate, and thereby applied to mass-produced members and the like. It has been found that a high-performance magnesium alloy having high strength and high elastic modulus can be produced without depending on the quenching method, which has been considered difficult.
本発明は、溶融マグネシウム中に、イットリウムを５原子％から１２原子％（５原子％≦Ｙ≦１２原子％）、亜鉛を１原子％から１２原子％（１原子％≦Ｚｎ≦１２原子％）投入し、公知の鋳造法により凝固させることでマグネシウム合金の強度と弾性率を向上させることを特徴とするものである。ここで、公知の鋳造法とは、例えば、ダイカスト法等の金型鋳造法、ロストワックス法等の砂型鋳造法などの鋳造法のことを意味する。 In the present invention, yttrium is contained in molten magnesium in an amount of 5 to 12 atom% (5 atom% ≦ Y ≦ 12 atom%), and zinc is 1 to 12 atom% (1 atom% ≦ Zn ≦ 12 atom%). The strength and elastic modulus of the magnesium alloy are improved by charging and solidifying by a known casting method. Here, the known casting method means, for example, a casting method such as a die casting method such as a die casting method or a sand casting method such as a lost wax method.
本発明では、高純度アルゴン雰囲気で、溶融マグネシウム中に、イットリウムを５原子％から１２原子％（５原子％≦Ｙ≦１２原子％）、より好ましくは、５原子％から８原子％（５原子％≦Ｙ≦８原子％）、亜鉛を１原子％から１２原子％（１原子％≦Ｚｎ≦１２原子％）、より好ましくは、１原子％から７原子％（１原子％≦Ｚｎ≦７原子％）投入し、公知の鋳造速度の５０Ｋ／秒未満という、冷却速度として、比較的遅い冷却速度を選択して凝固させることにより、マグネシウム合金内部に、マグネシウムとイットリウムと亜鉛により構成される金属間化合物（主に、Ｍｇ１２ＹＺｎであり、一部、マグネシウム、イットリウム、亜鉛の三層による長周期構造を有する）を析出させることが可能であり、その金属間化合物を合金内部に析出させることにより、強度の向上及び弾性率の向上が可能となる。 In the present invention, yttrium is contained in molten magnesium in a high purity argon atmosphere in an amount of 5 to 12 atomic% (5 atomic% ≦ Y ≦ 12 atomic%), more preferably 5 to 8 atomic% (5 atomic%). % ≦ Y ≦ 8 atomic%), zinc is 1 atomic% to 12 atomic% (1 atomic% ≦ Zn ≦ 12 atomic%), more preferably 1 atomic% to 7 atomic% (1 atomic% ≦ Zn ≦ 7 atomic) %), And by selecting a relatively slow cooling rate as a cooling rate of less than 50 K / sec, which is a known casting rate, and solidifying it, a magnesium alloy has a metal between magnesium, yttrium and zinc. compound (mainly, an Mg 12 YZn, some, magnesium, yttrium, having a long period structure of three layers of zinc) is possible to precipitate, alloy internal the intermetallic compound By depositing, thereby improving the improvement and modulus strength.
本発明は、マグネシウムへの固溶限界より大きい割合のイットリウム及び亜鉛を溶融マグネシウムに投入し、Ｍｇ１２ＹＺｎに代表される金属間化合物、特に、マグネシウム、イットリウム、亜鉛の三層による長周期構造を積極的に析出させ、マグネシウム合金材料の強化を図るものである。この場合、イットリウム及び亜鉛を１２原子％より多く添加すると、合金組成は、マトリクス部（後記する実施例１参照）のみにより形成される。マトリクス部のみにより合金が形成される場合、材料の巨視的な延性を期待できなくなるため、本発明では、Ｍｇ固溶体が発現する１２原子％以下に、イットリウム及び亜鉛の投入量を制限すべきである。また、イットリウムが５原子％未満及び亜鉛が１原子％未満では、Ｍｇ１２ＹＺｎに代表される金属間化合物が有効に析出しないため、イットリウム及び亜鉛の投入量は、それぞれ、５原子％以上及び１原子％以上とすべきである。 The present invention introduces yttrium and zinc in a proportion larger than the solid solution limit in magnesium into molten magnesium, and has an intermetallic compound typified by Mg 12 YZn, in particular, a long-period structure composed of three layers of magnesium, yttrium and zinc. It actively precipitates and strengthens the magnesium alloy material. In this case, when more than 12 atomic% of yttrium and zinc are added, the alloy composition is formed only by the matrix portion (see Example 1 described later). When the alloy is formed only by the matrix portion, macroscopic ductility of the material cannot be expected. Therefore, in the present invention, the amount of yttrium and zinc should be limited to 12 atomic% or less where the Mg solid solution is expressed. . In addition, when yttrium is less than 5 atomic% and zinc is less than 1 atomic%, an intermetallic compound typified by Mg 12 YZn is not effectively precipitated. Therefore, the amounts of yttrium and zinc input are 5 atomic% and 1 respectively. Should be at least atomic percent.
本発明の方法において、公知の鋳造法により凝固させるときの凝固速度は、好適には、５０Ｋ／秒未満であり、それにより、マトリックス部（金属間化合物内部）に、重元素（Ｙ或いはＺｎ）が偏析する層と他の層により構成されている６周期の長周期構造を有するマグネシウム合金を、効率よく作製することが可能となる。本発明により、純マグネシウムの弾性率（４１．３ＧＰａ：後記する表２の測定値）及び通常のマグネシウム合金の弾性率（約４４．３ＧＰａ）よりも高い値を有する高弾性率のマグネシウム合金、例えば、４６．３〜７１．６ＧＰａの弾性率のマグネシウム合金を作製することができる。また、本発明により、高硬度のマグネシウム合金、例えば、ビッカース硬度が、純マグネシウム（３１ＨＶ）の２．５倍を超える７９〜１１６ＨＶであるマグネシウム合金を作製することができる。 In the method of the present invention, the solidification rate when solidified by a known casting method is preferably less than 50 K / second, whereby heavy elements (Y or Zn) are contained in the matrix portion (inside the intermetallic compound). It is possible to efficiently produce a magnesium alloy having a six-period long-period structure composed of a layer that segregates and other layers. According to the present invention, a high-modulus magnesium alloy having a higher modulus than that of pure magnesium (41.3 GPa: measured value in Table 2 to be described later) and a normal magnesium alloy (approximately 44.3 GPa), for example, 46.3 to 71.6 GPa elastic modulus magnesium alloy can be produced. In addition, according to the present invention, a magnesium alloy having a high hardness, for example, a magnesium alloy having a Vickers hardness of 79 to 116 HV exceeding 2.5 times that of pure magnesium (31 HV) can be produced.
本発明により、（１）強度及び弾性率を向上させた高性能マグネシウム合金を製造することができる、（２）本発明の製造方法によれば、所定の合金添加によるマグネシウム合金を、公知の鋳造法により鋳込むだけで、マグネシウムとイットリウムと亜鉛による金属間化合物を析出させて、マグネシウム合金の強度と弾性率を向上させることができる、（３）本発明の製造方法は、鋳造特性を阻害するカルシウムやシリコン、リサイクル性を阻害するセラミックスを添加せずに、高性能マグネシウム合金の作製を可能にするものである、（４）本発明の高性能マグネシウム合金は、弾性率が高く、強度特性及び剛性特性がともに優れている、という格別の効果が奏される。 According to the present invention, (1) a high-performance magnesium alloy with improved strength and elastic modulus can be produced. (2) According to the production method of the present invention, a magnesium alloy with a predetermined alloy addition can be produced by known casting. It is possible to improve the strength and elastic modulus of the magnesium alloy by depositing an intermetallic compound of magnesium, yttrium and zinc simply by casting by the method. (3) The production method of the present invention hinders casting properties. (4) The high-performance magnesium alloy of the present invention has a high elastic modulus, strength characteristics, and the ability to produce a high-performance magnesium alloy without adding calcium, silicon, or ceramics that inhibit recyclability. An exceptional effect is that both the rigidity characteristics are excellent.
次に、実施例に基づいて本発明を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。 Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（マグネシウム合金の調製）
９９．９重量％のマグネシウム塊(１ｍｍ〜５ｍｍの粒状)、イットリウム塊（１ｍｍ〜７ｍｍの粒状）、亜鉛塊（３ｍｍ〜７ｍｍ）を、Ｍｇ−８原子％Ｙ−４原子％Ｚｎの割合で混合した。混合を終えた試料を、φ３０ｍｍ×Ｌ１５ｍｍの水冷式銅るつぼ内部に充填し、高純度アルゴン雰囲気で、アーク溶解・凝固させることにより、試料を作製した。作製した際の、溶解処理温度は９９３Ｋ、凝固速度は約１０Ｋ／ｓであった。
(Preparation of magnesium alloy)
Mix 99.9 wt% magnesium lump (1 mm to 5 mm granular), yttrium lump (1 mm to 7 mm granular), zinc lump (3 mm to 7 mm) in a ratio of Mg-8 atomic% Y-4 atomic% Zn. did. The sample after mixing was filled into a φ30 mm × L15 mm water-cooled copper crucible and arc-dissolved and solidified in a high-purity argon atmosphere to prepare the sample. When produced, the dissolution treatment temperature was 993 K, and the solidification rate was about 10 K / s.
（測定結果）
作製された試料の光学顕微鏡写真を、図１に示す。図１の観察結果及びＥＤＳ元素分析の結果から、鋳造された試料は、針状組織（マトリクス部）とＭｇ固溶体（デンドライト部：図１の白色部）により構成されており、マトリクス部の組成は、Ｍｇ：８０．１±１．０原子％、Ｙ：７．１±１．０原子％及びＺｎ：１２．８±１．０原子％であり、デンドライト部の組成は、Ｍｇ：９７．３±１．０原子％、Ｙ：２．７±１．０原子％及びＺｎ：０．１±１．０原子％であった。Ｘ線回折の結果、マトリクス部の組成は、主に、Ｍｇ１２ＹＺｎであり、他に、Ｍｇ２４Ｙ５、Ｍｇ３ＹＺｎ６も検出された。また、マトリクス部のＨＲ−ＴＥＭ観察により得られたＨＡＡＤＦ像を、図２に示す。このＨＡＡＤＦ像では、重元素が明るい像で示され、軽金属が暗い像で示される。図２から、マトリクス部内部に、マグネシウムと比較して重金属であるイットリウム又は亜鉛が、層状に存在し、６周期の長周期構造を構成していることが確認された。
(Measurement result)
An optical micrograph of the prepared sample is shown in FIG. From the observation results of FIG. 1 and the results of EDS elemental analysis, the cast sample is composed of a needle-like structure (matrix portion) and Mg solid solution (dendritic portion: white portion of FIG. 1), and the composition of the matrix portion is Mg: 80.1 ± 1.0 atomic%, Y: 7.1 ± 1.0 atomic% and Zn: 12.8 ± 1.0 atomic%, and the composition of the dendrite part is Mg: 97.3. They were ± 1.0 atomic%, Y: 2.7 ± 1.0 atomic%, and Zn: 0.1 ± 1.0 atomic%. As a result of X-ray diffraction, the composition of the matrix portion was mainly Mg 12 YZn. In addition, Mg 24 Y 5 and Mg 3 YZn 6 were also detected. FIG. 2 shows a HAADF image obtained by HR-TEM observation of the matrix portion. In this HAADF image, heavy elements are shown as bright images, and light metals are shown as dark images. From FIG. 2, it was confirmed that yttrium or zinc, which is a heavy metal compared to magnesium, is present in a layer form inside the matrix portion, and constitutes a six-period long-period structure.
表１に示される組成のマグネシウム合金を、実施例１と同様の手法で作製した。図１に示されるマトリクス部とデンドライト部の２相が確認された合金に関しては、表１の右端欄（「組織」欄）に、“２相”と記述した。それ以外の合金（「比較例２−１」）に関しては、同欄に、観察された相を記述した。イットリウム及び亜鉛を、１２原子％よりも多く添加すると、マトリクス相のみで合金は形成された。ある程度の延性を合金に付与するためには、イットリウム及び亜鉛の添加量を、１２原子％以下とするべきことが確認された。 Magnesium alloys having the compositions shown in Table 1 were produced in the same manner as in Example 1. Regarding the alloy in which two phases of the matrix portion and the dendrite portion shown in FIG. 1 are confirmed, “two phases” is described in the right end column (“structure” column) of Table 1. For the other alloys ("Comparative Example 2-1"), the observed phases are described in the same column. When more than 12 atomic percent of yttrium and zinc was added, an alloy was formed with only the matrix phase. In order to impart a certain degree of ductility to the alloy, it was confirmed that the addition amount of yttrium and zinc should be 12 atomic% or less.
実施例２で作製したマグネシウム合金群（実施例２−１から実施例２−６）に対して、大気中にて溶体化処理を実施した。処理温度は６７３Ｋ、処理時間は２４時間とした。処理後の試料組織を観察した結果、実施例２のものと比較して、試料中に大きな組織変化は確認できなかった。以上の結果より、凝固組織は、熱的に平衡組織であり、金型鋳造法、砂型鋳造法等の比較的冷却速度の遅い鋳造法でも、容易に作製可能であることが確認された。 Respect to the magnesium alloy group prepared in Example 2 (Working Examples 2-1 Example 2-6) was performed to solution treatment in the atmosphere. The processing temperature was 673 K and the processing time was 24 hours. As a result of observing the sample structure after the treatment, a large change in structure could not be confirmed in the sample as compared with that of Example 2. From the above results, it was confirmed that the solidified structure is a thermally balanced structure and can be easily produced even by a casting method having a relatively low cooling rate such as a die casting method and a sand casting method.
実施例２においてデンドライト部とマトリクス部が確認されたマグネシウム合金群（実施例２−１から実施例２−６）に対して、試料の弾性率を測定した。
（測定法）
測定法は、ビッカース型微小圧子による負荷−除荷試験を採用した。圧子を押し込む際の試験力は５０ｍＮ、押し込み速度は５ｍＮ／秒、押し込み後の保持時間は１０秒とした。除荷過程で測定される圧子の変位と試験力の傾きより、デンドライト部とマトリクス部の２相により構成される試料の弾性率を測定した。
Against dendrite portion and the matrix portion confirmed magnesium alloy group (Working Examples 2-1 Example 2-6) In Example 2, measuring the modulus of elasticity of the sample.
(Measurement method)
As the measurement method, a load-unloading test using a Vickers type micro indenter was adopted. The test force when pushing the indenter was 50 mN, the pushing speed was 5 mN / sec, and the holding time after pushing was 10 seconds. From the displacement of the indenter measured during the unloading process and the inclination of the test force, the elastic modulus of the sample composed of two phases of the dendrite part and the matrix part was measured.
(測定結果)
測定結果を、表２にまとめて示す。比較のため、純マグネシウム（９９％）で、同様の試験を実施した結果も示す。イットリウムの添加量を５原子％以上、亜鉛の添加量を１原子％以上とすることにより、マグネシウム合金の弾性率は５０ＧＰａよりも高い値を示した。なお、測定された純マグネシウムの弾性率は、４１．３ＧＰａであった。文献値（４４．３ＧＰａ）との差異は、実験誤差によるものと考慮される。
(Measurement result)
The measurement results are summarized in Table 2. For comparison, the result of carrying out a similar test with pure magnesium (99%) is also shown. By setting the addition amount of yttrium to 5 atom% or more and the addition amount of zinc to 1 atom% or more, the elastic modulus of the magnesium alloy showed a value higher than 50 GPa. The measured elastic modulus of pure magnesium was 41.3 GPa. The difference from the literature value (44.3 GPa) is considered to be due to experimental error.
実施例４において、５０ＧＰａより大きい弾性率を示し、マトリクス部とデンドライト部の２相で形成される試料（実施例４−１から４−６）について、試料のビッカース硬度を測定した。測定手法は、実施例４と同様である。すなわち、実施例４と同様の手法で作製した圧痕から、ビッカース硬度を算出した。その結果を、表３に示す。比較として、同様の手法で測定された、純マグネシウムの硬度も示す。純マグネシウムの硬度(３１ＨＶ)と比較して、本発明によるマグネシウム合金 (平均：９９ＨＶ)は、約３倍の硬度を有した。すなわち、本発明による合金は、純マグネシウム合金よりも高い強度を有することが確認された。 In Example 4, it shows the 50GPa greater modulus for the samples formed in a two-phase matrix portion and the dendrite section (4-6 Examples 4-1) was measured Vickers hardness of the sample. The measurement method is the same as that in Example 4. That is, the Vickers hardness was calculated from the indentation produced by the same method as in Example 4. The results are shown in Table 3. As a comparison, the hardness of pure magnesium measured by the same method is also shown. Compared to the hardness of pure magnesium (31 HV), the magnesium alloy according to the present invention (average: 99 HV) had a hardness about three times higher. That is, it was confirmed that the alloy according to the present invention has higher strength than the pure magnesium alloy.
以上詳述したように、本発明は、高性能マグネシウム合金及びその製造方法に係るものであり、本発明により、強度及び弾性率を向上させた高性能マグネシウム合金を製造することができる。本発明のマグネシウム合金は、弾性率が高く、強度特性及び剛性特性がともに優れた高性能マグネシウム合金であり、特定の合金添加によるマグネシウム合金を、公知の鋳造法により鋳込むだけで製造することができ、鋳造特性を阻害するカルシウムやシリコン、リサイクル性を阻害するセラミックスを添加する必要がない。本発明のマグネシウム合金は、自動車をはじめとする輸送機部品及び宇宙・航空機部品、電気・電子機器部品等の幅広い分野で利用することが可能な、次世代の構造用部材を提供するものとして有用である。 As described above in detail, the present invention relates to a high-performance magnesium alloy and a method for producing the same, and according to the present invention, a high-performance magnesium alloy with improved strength and elastic modulus can be produced. The magnesium alloy of the present invention is a high-performance magnesium alloy having a high modulus of elasticity and excellent strength and rigidity characteristics, and a magnesium alloy with a specific alloy addition can be produced simply by casting by a known casting method. This eliminates the need to add calcium and silicon that hinder casting properties and ceramics that hinder recycling. The magnesium alloy of the present invention is useful as a next-generation structural member that can be used in a wide range of fields such as transportation equipment parts including automobiles, space / aircraft parts, and electrical / electronic equipment parts. It is.
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| JP4792271B2 (en) * | 2005-10-13 | 2011-10-12 | 財団法人大阪産業振興機構 | Method for modifying alloy compact and alloy compact |
| DE102006015457A1 (en) | 2006-03-31 | 2007-10-04 | Biotronik Vi Patent Ag | Magnesium alloy and related manufacturing process |
| WO2010044320A1 (en) * | 2008-10-15 | 2010-04-22 | 国立大学法人 熊本大学 | Magnesium alloy and process for production thereof |
| JP2010095787A (en) * | 2008-10-20 | 2010-04-30 | Kumamoto Univ | Magnesium alloy and method for producing the same |
| JP2010095741A (en) * | 2008-10-15 | 2010-04-30 | Kumamoto Univ | Method for manufacturing magnesium alloy |
| JP2010185093A (en) * | 2009-02-10 | 2010-08-26 | Washi Kosan Co Ltd | Magnesium alloy raising young's modulus |
| JP5714436B2 (en) * | 2011-07-11 | 2015-05-07 | 株式会社神戸製鋼所 | Method for producing magnesium alloy material and magnesium alloy material produced thereby |
| CN113234978B (en) * | 2021-05-08 | 2022-04-29 | 合肥诺瓦新材料科技有限公司 | Extruded magnesium-yttrium alloy and preparation method thereof |
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2004
- 2004-01-27 JP JP2004019037A patent/JP4352127B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943738A (en) * | 2019-05-15 | 2019-06-28 | 湖南科技大学 | One kind magnesium-rare earth of high-modulus containing aluminium and preparation method thereof |
| CN109943738B (en) * | 2019-05-15 | 2021-09-14 | 湖南科技大学 | Aluminum-containing high-modulus rare earth magnesium alloy and preparation method thereof |
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