JP5429702B2 - Magnesium alloy and manufacturing method thereof - Google Patents
Magnesium alloy and manufacturing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
Description
本発明は、強度と靱性の良好な新しいマグネシウム合金とその製造方法に関するものである。 The present invention relates to a new magnesium alloy having good strength and toughness and a method for producing the same.
マグネシウム合金は、軽量であるという特長が注目されて各種構造部材への適用が期待されている。そして、実用化に向けての特性の改善が進められてもいる。特に、マグネシウム合金の機械構造材等としての実用化のためには、軽量であるという特長とともに、高い強度と靱性を持つものとすることが課題となる。 Magnesium alloys are expected to be applied to various structural members because of their light weight. And the improvement of the characteristic for practical use is also advanced. In particular, for practical use as a mechanical structure material of a magnesium alloy, it is a problem to have high strength and toughness as well as the feature of being lightweight.
この課題を解決するために、これまでにも様々な検討や工夫が試みられている。 In order to solve this problem, various studies and ideas have been attempted so far.
たとえば従来では、マグネシウム合金の高強度−高靱性特性を実現するための手段として、主に粉末や箔帯などを用い、その固化成形体を作成し、その後、温間ひずみ加工を導入することが一般的に試みられている。この方法での特徴は、結晶粒組織の微細化と同時に金属間化合物などの第二相粒子をマグネシウム母相に均一微細に分散させることである。 For example, conventionally, as a means for realizing the high strength-high toughness characteristics of a magnesium alloy, it is possible to create a solidified molded body mainly using powder or foil strips, and then introduce warm strain processing. It is generally attempted. The feature of this method is that the second phase particles such as intermetallic compounds are uniformly and finely dispersed in the magnesium matrix simultaneously with the refinement of the crystal grain structure.
しかし、これら従来の方法では、固化成形時に取り込んだ酸素が、粒界上に酸化化合物として存在する可能性があるため、特性劣化を招く恐れがある。また、過飽和合金の粉末や箔帯などを使用するため、温間加工中に容易に第二相粒子が析出し、粒子の体積率（特に低濃度側に）を制御することが難しいため、マグネシウム合金の強度−靱性は一定以上に向上することは困難とされていた。 However, in these conventional methods, there is a possibility that oxygen taken in at the time of solidification molding may exist as an oxide compound on the grain boundary, leading to deterioration of characteristics. Also, since supersaturated alloy powder and foil strips are used, second phase particles are easily precipitated during warm working, and it is difficult to control the volume fraction of the particles (especially on the low concentration side). It has been difficult to improve the strength-toughness of the alloy beyond a certain level.
たとえば、特許文献１（特開２００６−２１８４）の方法は、Ｍｇ−１〜８ＲＥ（ＲＥ：希土類元素）−１〜６Ｃａの合金の粉末固化体を作成し、次いで温間押出加工を行うものであるが、粉末固化体を作成する際に、母相と母相の界面に、酸化物の取り込みが考えられ、破壊靱性の向上は難しい。また、希土類金属を使用するため、素地の価格が高価になることが予測されるが、このような負担増に見合うだけの特性、機能の顕著な向上は期待し難い。 For example, the method of Patent Document 1 (Japanese Patent Laid-Open No. 2006-2184) is a method in which a powder solidified body of an alloy of Mg-1 to 8RE (RE: rare earth element) -1 to 6Ca is prepared, and then warm extrusion is performed. However, when forming a powder solidified body, it is considered that oxide is taken into the interface between the parent phase and the parent phase, and it is difficult to improve fracture toughness. In addition, since rare earth metals are used, the price of the substrate is expected to be expensive, but it is difficult to expect significant improvements in characteristics and functions to meet such an increased burden.
特許文献２（特開２００４−１４９８６２）は、Ｍｇ−Ｚｎ−ＲＥ系合金による高強度高靱性マグネシウム合金に関するものである。しかし、高濃度の異種元素を添加した溶湯を急冷凝固粉末とし、これを固化成形することにより、高体積率の析出物を均一分散させるものであって、金属間化合物の分散強化に依存しているため、高体積率の分散物と母相の界面などで容易に破壊が進展し、高靱性化ならびに高延性化が達成できないという問題点がある。さらに、希土類金属を使用するため、素地の価格が高価になるが、このような負担増に見合うだけの特性、機能の顕著な向上は期待し難い。 Patent document 2 (Unexamined-Japanese-Patent No. 2004-149862) is related with the high intensity | strength high toughness magnesium alloy by a Mg-Zn-RE type | system | group alloy. However, a molten metal added with a high concentration of different elements is used as a rapidly solidified powder, and by solidifying and molding this, a high volume fraction precipitate is uniformly dispersed, depending on the dispersion strengthening of the intermetallic compound. Therefore, there is a problem in that fracture easily progresses at the interface between the high volume fraction dispersion and the matrix phase, and high toughness and high ductility cannot be achieved. Furthermore, since rare earth metals are used, the price of the substrate becomes expensive, but it is difficult to expect significant improvements in characteristics and functions to meet such an increased burden.
また、特許文献３（特開平５−７０８８０）および特許文献４（特開平７−３３７５）は、高濃度の異種元素を添加した溶湯を急冷凝固箔体とし、その後、押出固化成形する製造法に係わるものである。 Further, Patent Document 3 (Japanese Patent Laid-Open No. 5-70880) and Patent Document 4 (Japanese Patent Laid-Open No. 7-3375) describe a manufacturing method in which a molten metal added with a high concentration of different elements is used as a rapidly solidified foil body and then extrusion solidified. It is related.
しかし、この方法では、金属間化合物の分散強化に依存しているため、高体積率の分散物と母相の界面などで容易に破壊が進展し、高靱性化ならびに高延性化が達成できない。また、固化成形を得るまで脱酸素雰囲気下で行うため、作業の簡便性を図ることができないという問題点がある。 However, since this method relies on dispersion strengthening of the intermetallic compound, fracture easily progresses at the interface between the high volume fraction dispersion and the matrix phase, and high toughness and high ductility cannot be achieved. In addition, since it is performed in a deoxygenated atmosphere until solidified molding is obtained, there is a problem that the convenience of work cannot be achieved.
特許文献５（特開平５−３０６４２４）は、Ｍｇ−ＲＥ系合金による高硬度・強度・靱性マグネシウム合金の製造手法に係わるものである。 Patent Document 5 (Japanese Patent Laid-Open No. 5-306424) relates to a method for producing a high hardness / strength / tough magnesium alloy using an Mg—RE alloy.
その手法と問題点は特許文献３、４の場合と同じである。 The method and problems thereof are the same as in Patent Documents 3 and 4.
一方、特許文献６（特開２００３−２７７８９９）は、鋳造マグネシウム合金に０．４以下の予歪みを加え、その後、温間ひずみ加工を施す製造方法に係わるものである。 On the other hand, patent document 6 (Unexamined-Japanese-Patent No. 2003-277899) is related to the manufacturing method which adds a pre-strain of 0.4 or less to a cast magnesium alloy, and performs a warm strain process after that.
この方法では、温間加工前に予歪みを加え、均一な析出核形成サイトを導入する。これによって、マグネシウム母相に微細分散粒子相を形成することを可能としている。 In this method, pre-strain is applied before warm working, and uniform precipitation nucleation sites are introduced. This makes it possible to form a finely dispersed particle phase in the magnesium matrix.
この特許文献６の方法は、粉末や箔体などからの固化成形体ではなく、鋳造マグネシウム合金を用いている点においてより実際的に合理的であるが、その手法は実用的には必ずしも制御、再現容易ではない。このため、マグネシウム母相への微細粒子分散の組織による強度−靱性の向上には大きな難点がある。 The method of Patent Document 6 is more practically rational in that a cast magnesium alloy is used instead of a solidified molded body such as a powder or a foil body, but the method is not necessarily controlled practically. It is not easy to reproduce. For this reason, there is a great difficulty in improving the strength-toughness due to the structure of fine particle dispersion in the magnesium matrix.
また、鋳造材を用いる手法としては、非特許文献１（Materials Transactions, 47(2006), 1066-1077)において、Ｍｇ−ＲＥ−Ｚｎ−Ｚｒ合金を用いた高靱性合金の製造が開示されている。この方法では、鋳造材を温間ひずみ加工により展伸化し、その後、熱処理を施し、第二相粒子などの析出物を母相に分散させている。 As a technique using a cast material, Non-Patent Document 1 (Materials Transactions, 47 (2006), 1066-1077) discloses the production of a high toughness alloy using an Mg—RE—Zn—Zr alloy. . In this method, the cast material is stretched by warm strain processing, and then heat treated to disperse precipitates such as second phase particles in the matrix.
しかし、温間ひずに加工後に熱処理を実施しているため、母相の結晶粒が粗大化し、高強度化が達成できないという問題がある。また、添加元素として希土類元素を用いるため、素地の価格が高価になることが予測されるが、このような負担増に見合うだけの特性、機能の向上は期待し難い。 However, since the heat treatment is carried out after processing in the warm strain, there is a problem that the crystal grains of the parent phase become coarse and high strength cannot be achieved. In addition, since rare earth elements are used as additive elements, the price of the substrate is expected to be expensive, but it is difficult to expect improvements in characteristics and functions to meet such an increased burden.
以上のような従来の技術においては、強度−靱性の特性の向上のために、マグネシウム母相に微細粒子を分散させた組織構成とするとの点において留意されるものであるが、このような組織構成の特徴を強度−靱性の向上へと発展させることは難しい。そこで、このための新しい技術手段の開発が必要とされている。その際の観点としては以下のことが考慮されねばならない。 In the conventional technology as described above, it is noted that the structure is a structure in which fine particles are dispersed in the magnesium matrix in order to improve the strength-toughness characteristics. It is difficult to develop structural features to improve strength-toughness. Therefore, it is necessary to develop new technical means for this purpose. The following points should be taken into consideration as the viewpoint at that time.
１）マグネシウム合金の組織構成として新しい発展的知見を提示していること。 1) Presenting new developmental knowledge as the structure of the magnesium alloy.
２）より簡便に実際的に実現されること。 2) To be realized more simply and practically.
３）希土類元素ではなく、比較的安価な添加元素を用いてのマグネシウム合金であること。 3) A magnesium alloy using a relatively inexpensive additive element, not a rare earth element.
４）増希土類元素を用いる場合には、経済的負担に見合う顕著な特性、機能の向上が図られること。 4) When using the rare earth elements, remarkable characteristics and functions should be improved to meet the economic burden.
このような観点については、本出願人においても、たとえば観点４）の希土類元素の使用の場合として、特許文献７（特開２００５−１１３２３５）のように、高強度で良好な延性を有し、特に高温強度の高いマグネシウム合金展伸材をすでに開発している。 About such a viewpoint, even in the present applicant, for example, in the case of using the rare earth element of the viewpoint 4), as in Patent Document 7 (Japanese Patent Laid-Open No. 2005-113235), it has high strength and good ductility, A magnesium alloy wrought material with particularly high temperature strength has already been developed.
このマグネシウム合金展伸材は、組成式Ｍｇ１００−（ａ＋ｂ）ＺｎａＹｂ（式中ａ、ｂは原子％であり、ａ/１２≦ｂ≦ａ/３、１．５≦ａ≦１０）で示される組成を有し、組成式Ｍｇ３Ｚｎ６Ｙで示される準結晶がマグネシウム母相（α−Ｍｇ）の結晶粒界に晶出し、かつ粒子径１００ｎｍ以下の準結晶とその近似結晶とがマグネシウム母相の結晶粒内に均一に分散した組織を有している。準結晶および近似結晶は２５０℃以下では相変態を起こさず安定であり、転位との強い相互作用により強度を著しく高め、マグネシウム母相の結晶粒界に位置する準結晶は高温において粒界すべり抑制し、これらの効果が相乗して高温強度が向上する。This magnesium alloy wrought material has a composition formula Mg 100- (a + b) Zn a Y b (where a and b are atomic%, a / 12 ≦ b ≦ a / 3, 1.5 ≦ a ≦ 10). And a quasicrystal having a composition formula Mg 3 Zn 6 Y crystallizes at the grain boundary of the magnesium parent phase (α-Mg), and a quasicrystal having a particle diameter of 100 nm or less and its approximate crystal Has a structure uniformly dispersed in the crystal grains of the magnesium matrix. Quasicrystals and approximate crystals are stable without causing phase transformation at temperatures below 250 ° C. The strength is remarkably increased by strong interaction with dislocations, and quasicrystals located at the grain boundaries of the magnesium matrix suppress grain boundary slip at high temperatures. However, these effects synergistically improve the high-temperature strength.
だが、上記マグネシウム合金展伸材は、引張変形時の強度および延性ならびに高温強度の改善に注力されて開発されたものであり、他の特性は明瞭ではない。車輌等の移動体用構造部材への適用を考慮すると、接触、衝突等に対する安全性や信頼性を確保する必要があり、そのためには高い圧縮変形能と優れた破壊靱性能を有することが非常に重要となる。 However, the magnesium alloy wrought material has been developed with a focus on improving strength and ductility during tensile deformation and high-temperature strength, and other characteristics are not clear. Considering application to structural members for moving bodies such as vehicles, it is necessary to ensure safety and reliability against contact, collision, etc. For that purpose, it is very important to have high compressive deformability and excellent fracture toughness performance. It becomes important to.
マグネシウム合金は、マグネシウム特有の結晶構造に起因して圧延、押出し等のひずみ加工を施すことにより、ひずみ加工時に形成される底面に配向する集合組織がそのまま材料中に残る。このため、これまでの市販のマグネシウム合金展伸材は、室温において高い引張強度を示す一方で、圧縮強度は、引張強度の５０％〜８０％程度に止まっている。したがって、一般的なマグネシウム合金展伸材を移動体用構造部材に適用した場合、圧縮ひずみが発生する箇所は強度が低く、形状の維持が難しくなる。また、マグネシウム母相に過度に準結晶および近似結晶が析出すると、準結晶および近似結晶が破壊の起点となり、破壊靱性が低下する恐れがある。 When a magnesium alloy is subjected to strain processing such as rolling or extrusion due to a crystal structure peculiar to magnesium, a texture oriented at the bottom formed during strain processing remains in the material as it is. For this reason, the commercially available magnesium alloy wrought material so far exhibits a high tensile strength at room temperature, while the compressive strength remains at about 50% to 80% of the tensile strength. Therefore, when a general magnesium alloy wrought material is applied to the structural member for a moving body, the portion where the compressive strain is generated has low strength and it is difficult to maintain the shape. Further, if the quasicrystal and the approximate crystal are excessively precipitated in the magnesium matrix, the quasicrystal and the approximate crystal may be the starting point of fracture, and the fracture toughness may be reduced.
さらに、上記マグネシウム合金展伸材は、上記組織が形成されるために、マグネシウム合金鋳造材を２３０℃〜４２０℃で加工率５０％以上の熱間加工を施した後、３７０℃〜４２０℃に１０分間〜１０時間保持し、次いで２０℃/秒以上の冷却速度で室温まで冷却する第１段階と、その後、１５０℃〜２５０℃に１時間〜１５時間保持後、室温まで冷却する第２段階とからなる熱処理を施して製造される。このように熱間加工後、二段階からなる熱処理を施すことは、工程が複雑であることが否めない。実用化技術とするためには工程の簡略化が望まれている。 Further, the magnesium alloy wrought material is subjected to hot working at a processing rate of 50% or more at 230 ° C. to 420 ° C. after the magnesium alloy cast material is formed at 370 ° C. to 420 ° C. A first stage of holding for 10 minutes to 10 hours and then cooling to room temperature at a cooling rate of 20 ° C./sec or more, and then a second stage of cooling to room temperature after holding at 150 ° C. to 250 ° C. for 1 hour to 15 hours It is manufactured by applying a heat treatment consisting of In this way, it is undeniable that the heat treatment consisting of two steps after the hot working is complicated. In order to make it a practical technology, simplification of the process is desired.
本発明は、以上のとおりの背景から、従来技術の問題点を解消し、
１）マグネシウム合金の組織構成として新しい発展的知見を提示し、
２）より簡便に実際的に実現可能で、
３）希土類元素ではなく、比較的安価な添加元素を用いてのマグネシウム合金として、高強度、高靱性な新しいマグネシウム合金とその製造方法を提供することを課題とし、また、
４）希土類元素を用いる場合には、その経済的負担増に見合うだけの顕著な特性、機能の向上が図られる、
との観点からの、高強度で高延性を有するとともに、圧縮強度および破壊靱性が高い新たなマグネシウム合金とこのマグネシウム合金を簡便に製造することのできる製造方法を提供することを課題としている。The present invention solves the problems of the prior art from the background as described above,
1) Presenting new developmental knowledge as the structure of magnesium alloy,
2) It can be realized more simply and practically,
3) As a magnesium alloy using a relatively inexpensive additive element instead of a rare earth element, an object is to provide a new magnesium alloy having high strength and high toughness and a method for producing the same,
4) When rare earth elements are used, remarkable characteristics and functions can be improved to meet the increased economic burden.
In view of the above, it is an object to provide a new magnesium alloy having high strength and high ductility, high compressive strength and high fracture toughness, and a production method capable of easily producing the magnesium alloy.
本発明のマグネシウム合金は、上記の課題を解決するために、以下のことを特徴としている。 In order to solve the above problems, the magnesium alloy of the present invention is characterized by the following.
第１：合金組成が次式；
Ｍｇ １００−ａ Ｚｎ ａ （ａは原子％を示し、１．６≦ａ≦８．０である）で表わされ、マグネシウム母相中に少なくとも亜鉛を含み、球状で、平均粒径が５００ｎｍ以下である第二相粒子が析出しているマグネシウム合金であって、当該マグネシウム母相の平均結晶粒径は１５μｍ以下であり、第二相粒子のアスペクト比が５：１以下であることを特徴とするマグネシウム合金である。
1: the alloy composition is
Mg 100-a Zn a (wherein a represents atomic% and 1.6 ≦ a ≦ 8.0), the magnesium matrix contains at least zinc, is spherical, and has an average particle size of 500 nm or less Wherein the second phase particles are precipitated, wherein the magnesium matrix has an average crystal grain size of 15 μm or less, and the second phase particles have an aspect ratio of 5: 1 or less. Magnesium alloy.
第２：合金組成が次式；
Ｍｇ１００−（ａ＋ｂ）Ｚｎａ Ｃａ ｂ
（ａ、ｂは原子％を示し、０＜ｂ≦５．７において、０．３≦ａ≦８．５であることを示す。）
で表わされ、マグネシウム母相中に、少なくとも亜鉛を含み、球状で、平均粒径が５００ｎｍ以下である第二相粒子が析出しているマグネシウム合金であって、当該マグネシウム母相の平均結晶粒径は１５μｍ以下であり、第二相粒子のアスペクト比が５：１以下であることを特徴とするマグネシウム合金である。
Second: Alloy composition is the following formula:
Mg 100- (a + b) Zn a Ca b
(A and b represent atomic%, and in 0 <b ≦ 5.7, 0.3 ≦ a ≦ 8.5.)
A magnesium alloy in which second phase particles containing at least zinc and having a spherical shape and an average particle size of 500 nm or less are precipitated in the magnesium matrix, and the average crystal grains of the magnesium matrix The magnesium alloy is characterized in that the diameter is 15 μm or less and the aspect ratio of the second phase particles is 5: 1 or less .
第３：次式で表わされる第二相粒子の平均粒子径とマグネシウム母相の平均結晶粒子径との比ＫＡが０．００５以上０．２以下である。Third: the ratio K A between the average mean crystal grain size of the particle diameter and the magnesium mother phase of the second phase particles represented by the following formula is from 0.005 to 0.2.
ＫＡ＝第二相粒子の平均粒子径／マグネシウム母相の
平均結晶粒子径
第４：亜鉛の含有量が、１．６≦ａ≦３．５の範囲内である。K A = average particle diameter of second phase particles / magnesium matrix phase
Average crystal particle diameter 4: The zinc content is in the range of 1.6 ≦ a ≦ 3.5.
上記第１から第４の発明のマグネシウム合金は、添加元素として希土類元素を使用せずに、マグネシウム母相に亜鉛を含む第二相粒子が析出され、この第二相粒子が球状でナノサイズの平均粒径を有しているという組成と組織の構成によって、従来とは全く異なる知見に基づく合金として強度、靱性の顕著な向上を可能としている。 In the magnesium alloys of the first to fourth inventions, second phase particles containing zinc are precipitated in the magnesium matrix without using rare earth elements as additive elements, and the second phase particles are spherical and nano-sized. The composition having the average particle size and the structure of the structure enable the strength and toughness to be remarkably improved as an alloy based on knowledge completely different from the conventional one.
第二相の析出粒子は分散強化型粒子として作用し、マグネシウム母相の結晶粒微細化に起因した強度改善だけでなく、更なる高強度化が可能とされる。そして、球状な第二相析出粒子は、変形中に生じる転位の運動をより多く固着することが可能であり、高強度化と高靱性化が図られる。 The precipitated particles of the second phase act as dispersion strengthened particles, and not only the strength improvement due to the refinement of the crystal grains of the magnesium matrix but also the further enhancement of strength is possible. The spherical second-phase precipitated particles can fix more dislocation movements that occur during deformation, and can achieve high strength and high toughness.
マグネシウム母相の結晶粒の微細化によって、破壊の起点となる変形双晶の発生を抑制でき、その結果、高い延性と高い破壊靱性も得られる。 By making the crystal grains of the magnesium matrix finer, it is possible to suppress the generation of deformation twins that are the starting point of fracture, and as a result, high ductility and high fracture toughness are also obtained.
本発明の希土類元素を含有しないマグネシウム合金においては、その組成として、マグネシウムと亜鉛、もしくはマグネシウムと亜鉛、そしてさらに非希土類元素からなるものとして特定される。このマグネシウム合金において、前記のとおり、マグネシウム母相中に少くとも亜鉛を含む第二相粒子が析出されており、この第二相粒子は球状で、その平均粒子系はナノサイズである。 In the magnesium alloy containing no rare earth element of the present invention, the composition is specified as consisting of magnesium and zinc, or magnesium and zinc, and further a non-rare earth element. In this magnesium alloy, as described above, second-phase particles containing at least zinc are precipitated in the magnesium matrix, the second-phase particles are spherical, and the average particle system is nano-sized.
ここで、第二相粒子は、合金構成元素の金属間化合物、あるいは合金や混合相にあるものとして考慮される。いずれの場合においても、この第二相粒子を構成する少くとも一つの元素種は亜鉛である。このような第二相粒子が「球状」であるとのことは、本発明では、真球状だけでなく、結晶粒子の長軸と短軸とのアスペクト比が、長軸長さ：短軸長さとして１０：１以下の範囲にあるものとして定義される。またその平均粒径が「ナノサイズ」であるとのことは、１μｍ未満、より具体的には５００ｎｍ以下であることとして定義される。 Here, the second phase particles are considered as being in an intermetallic compound of an alloy constituent element, an alloy or a mixed phase. In any case, at least one element species constituting the second phase particle is zinc. In the present invention, such second phase particles are “spherical”. In the present invention, the aspect ratio between the major axis and the minor axis of the crystal particle is not only true spherical, but the major axis length: minor axis length. It is defined as being in the range of 10: 1 or less. Moreover, that the average particle diameter is “nano-size” is defined as being less than 1 μm, more specifically 500 nm or less.
マグネシウム母相に１ミクロン以上の析出粒子が存在する場合には、変形中、界面で応力集中が発生し破壊の起点となりやすい。また、アスペクト比が１０：１以上の針状、あるいは柱状品の場合も同様である。そのため、高強度化が期待できないだけでなく、高靱性化ならびに高延性化の達成が難しい。 When precipitated particles of 1 micron or more are present in the magnesium matrix, stress concentration occurs at the interface during deformation, which tends to be the starting point of fracture. The same applies to needle-shaped or columnar products having an aspect ratio of 10: 1 or more. Therefore, not only high strength cannot be expected, but it is difficult to achieve high toughness and high ductility.
なお、マグネシウム母相の粒界上に第二相の析出粒子が存在する可能性がある。 In addition, there is a possibility that precipitated particles of the second phase exist on the grain boundary of the magnesium matrix.
粒界上に存在する析出粒子は、変形の連続性を保つことが難しく、高強度化は期待できるが、高靱性化ならびに高延性化の達成がその存在の増大とともに難しくなるため、粒界上に存在する析出粒子が極力少ない方が望ましい。 Precipitated particles existing on the grain boundaries are difficult to maintain the continuity of deformation, and high strength can be expected. However, it is difficult to achieve high toughness and high ductility as the presence of the particles increases. It is desirable that the amount of precipitated particles present in the is as small as possible.
本発明では、上記のアスペクト比は、より好適には５：１以下、そしてナノサイズの平均粒径については好適には１００ｎｍ以下であることが考慮される。 In the present invention, it is considered that the aspect ratio is more preferably 5: 1 or less, and the nano-sized average particle diameter is preferably 100 nm or less.
そして、第二相粒子の析出の密度に係わる体積率については、一般的には最大体積率として１０％以下、また、粒子の心心間隔については一般的に１００〜３００ｎｍの範囲にあることが好適に考慮される。 The volume ratio related to the density of precipitation of the second phase particles is generally 10% or less as the maximum volume ratio, and the center-to-center distance of the particles is preferably in the range of 100 to 300 nm. To be considered.
マグネシウム母相は、主としてマグネシウムからなる相であるが、他の合金元素を固溶してもよい。このようなマグネシウム母相は、その結晶粒径は微細であることが好ましく、通常は、平均粒径として１５μｍ以下、より好適には、合金特性の観点において５μｍ以下であることが考慮される。結晶粒微細化により、引張強度の増加が期待できる。また、変形過程において、非底面転位と粒界すべりの活動が可能になるため、破壊の起点となる変形双晶の発生を抑制することにつながり、引張延性が飛躍的に向上する。 The magnesium matrix is a phase mainly composed of magnesium, but other alloy elements may be dissolved. Such a magnesium parent phase preferably has a fine crystal grain size, and is usually considered to have an average grain size of 15 μm or less, and more preferably 5 μm or less in terms of alloy characteristics. An increase in tensile strength can be expected by refining crystal grains. In addition, in the deformation process, non-bottom dislocations and grain boundary sliding are possible, which leads to the suppression of the generation of deformation twins that are the starting point of fracture, and dramatically improves the tensile ductility.
第二相粒子の平均粒子径とマグネシウム母相の平均粒子径との比は、前記式でのＫＡ値として、０．００５〜０．２の範囲内とするのが好ましい。The ratio between the average mean particle diameter of the particle size and magnesium mother phase of the second phase particles, as K A value of the above formula, preferably in the range of 0.005 to 0.2.
合金の組成としては、たとえば前記のとおりの、合金組成が次式；
Ｍｇ１００−（a＋b）ＺｎaＭｂ
（Ｍは非希土類元素の１種以上を示し、ａ、ｂは原子％を示し、ｂ＝０において、１．６≦ａ≦８．０であり、０＜ｂ≦５．７において、０．３≦ａ≦８．５であることを示す。）
で表わされるものとすることが好適に考慮される。平均粒径が５００ｎｍ以下の第二母相粒子の最大体積率１０％以下とする場合として考慮される。さらには、ここで、亜鉛の含有量が、１．６≦ａ≦３．５の範囲内であることが好ましい。As the composition of the alloy, for example, as described above, the alloy composition has the following formula:
Mg 100- (a + b) Zn a M b
(M represents one or more non-rare earth elements, a and b represent atomic%, 1.6 ≦ a ≦ 8.0 when b = 0, and 0.00 when 0 <b ≦ 5.7. 3 ≦ a ≦ 8.5.)
Is preferably taken into account. This is considered as a case where the maximum volume ratio of the second matrix phase particles having an average particle diameter of 500 nm or less is 10% or less. Further, the zinc content is preferably in the range of 1.6 ≦ a ≦ 3.5.
亜鉛の添加量が１．６ａｔ．％以下だと、析出物の形成が難しくなる傾向にある。 The amount of zinc added is 1.6 at. If it is less than or equal to%, formation of precipitates tends to be difficult.
また、３．５ａｔ．％以上を超えると、Ｍｇ−Ｚｎからなる析出物が多量に存在し、破壊の起点となりうる可能性が高く、本発明の効果ならびに高延性を期待することが難しくなる傾向にある。 Also, 3.5 at. If it exceeds 50% or more, a large amount of precipitates composed of Mg—Zn exist, which is likely to be the starting point of fracture, and it tends to be difficult to expect the effects of the present invention and high ductility.
亜鉛以外の非希土類原子を添加する場合には、母相となるマグネシウムに固溶し得る元素から選択する。その範囲としてはアルカリ土類金属、遷移金属のうちの１種以上とすることができる。たとえば、このような非希土類元素としては、Ｚｒ、Ｃａ、Ｓｒ、Ｂａ、Ａｌ等が例示される。 When non-rare earth atoms other than zinc are added, the element is selected from elements that can be dissolved in magnesium as a parent phase. The range can be one or more of alkaline earth metals and transition metals. For example, examples of such non-rare earth elements include Zr, Ca, Sr, Ba, and Al.
これらの非希土類元素の添加は、第二相粒子を短時間ですみやかに高密度に析出分散させる作用を有するものとして考慮される。 The addition of these non-rare earth elements is considered as having the action of precipitating and dispersing the second phase particles quickly and densely in a short time.
希土類元素を亜鉛とともにその合成組成において含有する本発明のマグネシウム合金においては、マグネシウム母相の結晶粒内のみに準結晶粒子相が析出分散されている。そして、この準結晶粒子相は、球状で、その平均粒径はナノサイズである。 In the magnesium alloy of the present invention containing the rare earth element together with zinc in its synthetic composition, the quasicrystalline particle phase is precipitated and dispersed only in the crystal grains of the magnesium parent phase. The quasicrystalline particle phase is spherical and the average particle size is nano-sized.
ここで、マグネシウム母相、「球状」、「ナノサイズ」の用語についての本発明での定義は前記の非希土類元素のマグネシウム合金の場合と同様である。なお、「準結晶粒子相」は、すでにその組成がＭｇ３Ｚｎ６ＲＥとして知られているものであるが、本発明においては、これに近似の安定相も含まれてよい。Here, the definitions in the present invention regarding the terms of the magnesium matrix, “spherical” and “nanosize” are the same as in the case of the magnesium alloy of the non-rare earth element. In addition, although the composition of the “quasicrystalline particle phase” is already known as Mg 3 Zn 6 RE, an approximate stable phase may be included in the present invention.
本発明での準結晶粒子相は、実質的に、マグネシウム母相の結晶粒内のみに存在し、その粒界には存在していない。このことは、本発明の最も大きな、そして極めて重要な特徴であり、発明の必須の構成要件でもある。 In the present invention, the quasicrystalline particle phase substantially exists only within the crystal grains of the magnesium matrix, and does not exist at the grain boundaries. This is the greatest and extremely important feature of the present invention and is an essential component of the invention.
より好適には、希土類元素含有の本発明のマグネシウム合金展伸材は、組成式Ｍｇ１００−（ｙ＋ｘ）ＺｎｙＲＥｘ（式中、ＲＥは、Ｙ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒのいずれか一種の希土類元素、ｘ、ｙはそれぞれ原子％であり、０．２≦ｘ≦１．５、５ｘ≦ｙ≦７ｘ）で示される組成を有し、平均結晶粒径が５μｍ以下のマグネシウム母相に、組成式Ｍｇ３Ｚｎ６ＲＥで示される組成を有し、母相結晶粒内に平均粒子径が０．２μｍ以下の準結晶粒子相が整合な界面を持って均一に分散した組織を有する。More preferably, the magnesium alloy wrought material of the present invention containing a rare earth element has a composition formula Mg 100- (y + x) Zn y RE x (where RE is Y, Gd, Tb, Dy, Ho, Er). Any one kind of rare earth elements, x and y are atomic%, 0.2 ≦ x ≦ 1.5, 5x ≦ y ≦ 7x), and magnesium having an average crystal grain size of 5 μm or less A structure in which a quasicrystalline particle phase having a composition represented by the composition formula Mg 3 Zn 6 RE in the parent phase and having an average particle size of 0.2 μm or less is uniformly dispersed with a consistent interface in the mother phase crystal grains Have
この場合の本発明のマグネシウム合金は、Ｍｇ−Ｚｎ−ＲＥの三元系の合金組成を有し、ＲＥには、Ｙの他、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒを含めた希土類元素のいずれか一種が好適に選択される。 In this case, the magnesium alloy of the present invention has an Mg—Zn—RE ternary alloy composition, and RE includes any of rare earth elements including Y, Gd, Tb, Dy, Ho, and Er. One kind is suitably selected.
ＲＥの原子％ｘは、Ｙ、Ｇｄ、Ｔｂ、Ｄｙ、ＨｏおよびＥｒに共通であり、好ましくは０．２≦ｘ≦１．５である。ＲＥの原子％ｘが０．２原子％未満であると、準結晶粒子相の晶出が少な過ぎて高強度・高靭性化が実現されにくい。１．５原子％を超えると、準結晶粒子相の晶出が多くなり過ぎて準結晶粒子相が破壊の起点となり、延性および破壊靱性が低下する傾向にある。 The atomic% x of RE is common to Y, Gd, Tb, Dy, Ho, and Er, and preferably 0.2 ≦ x ≦ 1.5. If the RE atomic percent x is less than 0.2 atomic percent, the crystallization of the quasicrystalline particle phase is too small to achieve high strength and high toughness. When it exceeds 1.5 atomic%, the crystallization of the quasicrystalline particle phase becomes excessive, and the quasicrystalline particle phase becomes the starting point of fracture, and the ductility and fracture toughness tend to be lowered.
Ｚｎの原子％ｙはＲＥの原子％ｘに基づいて決まり、好ましくは５ｘ≦ｙ≦７ｘである。Ｚｎの原子％ｙが５ｘ未満であると、Ｍｇ３Ｚｎ６ＲＥの組成からなる準結晶粒子相の形成が難しくなる。７ｘを超えると、準結晶粒子相その他の金属間化合物（たとえばＭｇＺｎ２など）が多数晶出し、それらが変形過程の破壊の起点となり、特性劣化につながりやすい。The atomic% y of Zn is determined based on the atomic% x of RE, and preferably 5x ≦ y ≦ 7x. When the atomic% y of Zn is less than 5x, it becomes difficult to form a quasicrystalline particle phase having a composition of Mg 3 Zn 6 RE. If it exceeds 7x, a large number of quasicrystalline particle phases and other intermetallic compounds (for example, MgZn 2 ) are crystallized, which become the starting point of the destruction of the deformation process, and tend to lead to characteristic deterioration.
本発明のマグネシウム合金の組織は、平均結晶粒径が５μｍ以下のマグネシウム母相に、組成式Ｍｇ３Ｚｎ６ＲＥで示される組成を有し、母相結晶粒内に平均粒子径が０．２μｍ以下の準結晶粒子相が整合な界面を持って均一に分散した組織である。このような組織によって、室温引張強度とともに室温圧縮強度が高まる。圧縮降伏強度（σｃｙｓ）を引張降伏強度（σｔｙｓ）の８割以上（σｃｙｓ≧０．８σｔｙｓ）にすることができる。また、変形過程において、非底面転位の活動が可能になり、破壊の起点となる変形双晶の発生を抑制することができ、その結果、高い延性と高い破壊靱性が得られる。特に、準結晶粒子相がマグネシウム母相と整合な界面を持っているため、変形の連続性を良好に保つことができ、界面への応力集中が緩和され、高延性および高靱性化が可能となる。The structure of the magnesium alloy of the present invention has a composition represented by the composition formula Mg 3 Zn 6 RE in a magnesium matrix having an average crystal grain size of 5 μm or less, and an average grain size of 0.2 μm in the matrix crystal grains. The following quasicrystalline particle phase has a uniform interface with a consistent interface. Such a structure increases room temperature compressive strength as well as room temperature tensile strength. It can be the compression yield strength (sigma cys) Tensile yield strength (sigma tys) 8% or more of (σ cys ≧ 0.8σ tys). Further, in the deformation process, the activity of non-bottom dislocations becomes possible, and the generation of deformation twins that become the starting point of fracture can be suppressed. As a result, high ductility and high fracture toughness can be obtained. In particular, since the quasicrystalline particle phase has an interface that is consistent with the magnesium matrix phase, the continuity of deformation can be maintained well, stress concentration at the interface is relaxed, and high ductility and toughness can be achieved. Become.
商用高強度アルミニウム合金と同等の２５ＭＰａ・ｍ１/２以上の平面ひずみ破壊靱性値が可能となる。したがって、移動体用構造部材に適用する場合の接触、衝突等の際の安全性や信頼性が確保され、マグネシウム合金展伸材の移動体用構造部材への適用がより現実的になる。商用高強度アルミニウム合金材料の代替材料の候補となり得る。A plane strain fracture toughness value of 25 MPa · m 1/2 or more equivalent to a commercial high-strength aluminum alloy becomes possible. Therefore, the safety and reliability at the time of contact, collision and the like when applied to the structural member for moving body are ensured, and the application of the magnesium alloy stretched material to the structural member for moving body becomes more realistic. Can be a candidate for alternative materials for commercial high-strength aluminum alloy materials.
マグネシウム母相の平均粒子径が５μｍを超えると、変形双晶の発生を抑制することが困難で、高延性・高靭性を達成することが難しくなる。 When the average particle diameter of the magnesium matrix exceeds 5 μm, it is difficult to suppress the generation of deformation twins, and it becomes difficult to achieve high ductility and high toughness.
平均粒子径が０．２μｍ以下でマグネシウム母相に均一に分散する準結晶粒子相は、分散強化型粒子として作用し、マグネシウム合金展伸材のさらなる高強度化を実現する。 The quasicrystalline particle phase having an average particle size of 0.2 μm or less and uniformly dispersed in the magnesium matrix acts as a dispersion strengthening type particle, and further enhances the strength of the magnesium alloy wrought material.
準結晶粒子相の平均粒子径が０．２μｍを超えると、準結晶粒子相が変形過程で割れ、破壊の起点となりやすい。好ましくは、微細粒子相の平均粒子径とマグネシウム母相の平均結晶粒径との比、すなわち前記式により求められる値ＫＢが、
ＫＢ＝準結晶粒子相の平均粒子径/マグネシウム母相の平均結晶粒径として、０．０１以上０．２以下である。この範囲内にあれば、変形過程での割れを十分抑制することができる。When the average particle diameter of the quasicrystalline particle phase exceeds 0.2 μm, the quasicrystalline particle phase is likely to crack during the deformation process and become a starting point of fracture. Preferably, the ratio of the average crystal grain size of the average of the fine particle phase particle size and magnesium matrix, i.e. the value K B obtained by the equation,
K B = average particle size of quasicrystalline particle phase / average crystal particle size of magnesium parent phase is 0.01 or more and 0.2 or less. If it exists in this range, the crack in a deformation | transformation process can fully be suppressed.
なお、準結晶粒子相の体積割合や、その心心間隔については前記の非希土類元素合金の場合と同様に考慮することができる。 The volume fraction of the quasicrystalline particle phase and the center-to-center distance can be considered in the same manner as in the case of the non-rare earth element alloy.
本発明の準結晶粒子相は、上記の通り、マグネシウム母相と整合な界面を持っている。整合な界面を持つことにより変形の連続性を良好に保つことができ、界面への応力集中を緩和することができる。これは高延性および高破壊靱性に寄与する。２５ＭＰａ・ｍ１/2以上の高い平面ひずみ破壊靱性値が得られる。準結晶粒子相とマグネシウム母相との界面が非整合であると、変形がマグネシウム母相と準結晶粒相の界面で容易に断たれ、連続性を保つことができなくなり、その界面に応力集中が発生し、破壊の起点となる。延性および破壊靱性が低下する。As described above, the quasicrystalline particle phase of the present invention has an interface consistent with the magnesium matrix phase. By having a consistent interface, the continuity of deformation can be kept good, and stress concentration on the interface can be relaxed. This contributes to high ductility and high fracture toughness. A high plane strain fracture toughness value of 25 MPa · m 1/2 or more can be obtained. If the interface between the quasicrystalline particle phase and the magnesium matrix phase is inconsistent, deformation is easily cut off at the interface between the magnesium matrix phase and the quasicrystalline phase, and continuity cannot be maintained. Occurs and becomes the starting point of destruction. Ductility and fracture toughness are reduced.
以上のとおりの本発明のマグネシウム合金については、非希土類系、および希土類系のいずれの場合にも、上記組成を有するマグネシウム合金を溶解し、固化させて得られた母材に均質化処理を施した後に、温間温度域でひずみ加工を施すことにより製造される。 As for the magnesium alloy of the present invention as described above, in both the non-rare earth system and the rare earth system, the base material obtained by melting and solidifying the magnesium alloy having the above composition is subjected to a homogenization treatment. Then, it is manufactured by applying strain processing in the warm temperature range.
ここで、溶製（鋳造）後の母材に対しての均質化処理が本発明の方法にとって必須である。この均質化処理は、溶製（鋳造）後の固化組織がその後の温間ひずみ加工において残存しないようにすること、そして第二相粒子、あるいは準結晶粒子相を形成することを目的としている。この均質化処理は母材を加熱することにより行うが、この際の加熱温度は、通常は、母材の再結晶化温度未満であって、第二相粒子、あるいは準結晶粒子の形成度合、そして加熱のための時間を考慮して定めることができる。 Here, a homogenization treatment for the base material after melting (casting) is essential for the method of the present invention. The purpose of this homogenization treatment is to prevent the solidified structure after melting (casting) from remaining in the subsequent warm strain processing, and to form second phase particles or quasicrystalline particle phases. This homogenization treatment is performed by heating the base material, and the heating temperature at this time is usually lower than the recrystallization temperature of the base material, and the degree of formation of second phase particles or quasicrystalline particles, It can be determined in consideration of the time for heating.
均質化処理のための加熱温度、加熱時間は、合金の組成、そして所定の組織や特性レベルを考慮して定めることができるが、一般的目安としては、２００℃〜５００℃の温度範囲で、２〜５０時間の範囲である。 The heating temperature and heating time for the homogenization treatment can be determined in consideration of the composition of the alloy and a predetermined structure and characteristic level, but as a general guideline, a temperature range of 200 ° C. to 500 ° C. The range is 2 to 50 hours.
以上のような均質化処理を行わない場合には本発明のマグネシウム合金の実現は困難である。第二相粒子、そして準結晶粒子相について、球状でナノサイズのものとならに針状、あるいは板状の粒子が混在してしまい、その特性において、不都合が生じ、本発明の所期目的の実現は困難となる。 If the homogenization treatment as described above is not performed, it is difficult to realize the magnesium alloy of the present invention. As for the second phase particles and the quasicrystalline particle phase, needle-like or plate-like particles are mixed in addition to spherical and nano-sized particles, resulting in inconveniences in the characteristics, and the intended purpose of the present invention. Realization is difficult.
また、本発明の製造方法では、均質化処理後の温間温度域でのひずみ加工が必須である。 Moreover, in the manufacturing method of this invention, the distortion process in the warm temperature range after a homogenization process is essential.
ここでの「温間温度域」の温度範囲については、いわゆる「熱間加工」での再結晶温度以上での加工のように積極的に変形抵抗を低くして加工硬化を起こす場合のような温度域を意味してはいない。つまり、加熱することによって、マグネシウム母相の結晶粒径を所要範囲のものとし、球状でナイサイズ平均粒径の第二相粒子、もしくは準結晶粒子相を所要のものとするためのひずみ加工のための加熱温度範囲であると定義される。具体的には、再結晶化温度未満の温度であることが一般的目安となる。ただ、合金の組成や所定の特性によっては、それ以上であることも考慮される。 As for the temperature range of the “warm temperature range” here, as in the case of processing at a temperature higher than the recrystallization temperature in so-called “hot processing”, the deformation resistance is actively lowered to cause work hardening. It does not mean temperature range. In other words, by heating, the crystal grain size of the magnesium matrix is within the required range, and strain processing is performed to make the second phase particles with a spherical, nysize average particle size, or the quasicrystalline particle phase required. It is defined as a heating temperature range for. Specifically, a general guideline is a temperature lower than the recrystallization temperature. However, depending on the composition of the alloy and the predetermined characteristics, it is also considered that it is more than that.
一般的には１５０℃〜４００℃の温度範囲が考慮される。 Generally, a temperature range of 150 ° C to 400 ° C is considered.
そして、ひずみ加工については、あらかじめ加工時の温度と同等の温度に所要時間保持（熱処理）した後にひずみ加工を施すことが望ましい。ここでの保持時間は、母材全体に加工時温度が行き渡るのに要する時間として考慮される。母材の組成、大きさによっても相違するが、一般的には１０分間〜２時間程度である。 As for strain processing, it is desirable to perform strain processing after holding (heat treatment) for a required time at a temperature equivalent to the processing temperature in advance. The holding time here is considered as the time required for the processing temperature to reach the entire base material. Although it varies depending on the composition and size of the base material, it is generally about 10 minutes to 2 hours.
ひずみ加工時の加工度については、所定の合金組織とするための範囲として考慮される。一般的には５：１以上であって、たとえば５：１〜３０：１程度が目安として考慮される。 The degree of processing at the time of strain processing is considered as a range for obtaining a predetermined alloy structure. Generally, it is 5: 1 or more, for example, about 5: 1 to 30: 1 is considered as a standard.
合金の組成や特性によって適宜に定めることができるが、たとえば以下の実際的プロセスや条件を目安として考慮することができる。 Although it can be appropriately determined depending on the composition and characteristics of the alloy, for example, the following practical processes and conditions can be considered as a guide.
＜１＞加熱炉中に３００℃〜５００℃の温度範囲に保持して溶製材の均質化処理を行う。 <1> The molten material is homogenized while being maintained in a temperature range of 300 ° C. to 500 ° C. in a heating furnace.
＜２＞組織を一旦凍結させて安定化を図るための焼入れを行う。 <2> Quenching is performed to freeze the tissue and stabilize it.
＜３＞ひずみ加工用のビレットを機械加工で形成する。 <3> A billet for strain processing is formed by machining.
＜４＞１５０℃〜４００℃の温度範囲にて押出し、圧延、スウェージングなどのひずみ加工を行う。 <4> Extrusion in a temperature range of 150 ° C. to 400 ° C., and strain processing such as rolling and swaging.
もちろん、以上の形態に限られることはない。 Of course, it is not restricted to the above form.
そして、本発明では、希土類元素含有の合金の場合として、より好適には、溶製後に、４６０℃以下、４時間以上の条件で均質化処理を施し、ひずみ加工後にマグネシウム母相の大きさが５μｍ以下になる温度で、母材全体がその温度に行き渡るのに要する時間保持した後、温間温度以上で加工比８：１以上のひずみ加工を施す。 In the present invention, as an alloy containing a rare earth element, more preferably, after melting, homogenization treatment is performed under conditions of 460 ° C. or less and 4 hours or more, and the size of the magnesium matrix phase is increased after strain processing. After holding the time required for the whole base material to reach the temperature at a temperature of 5 μm or less, strain processing is performed at a processing ratio of 8: 1 or more at a temperature higher than the warm temperature.
母材の作製についても特に制限はない。たとえば、Ｍｇ、ＺｎおよびＲＥの各金属を原料として上記組成の範囲内で配合し、溶解後、鋳造等により固化させて母材を作製することができる。 There is no particular limitation on the production of the base material. For example, Mg, Zn, and RE metals can be mixed as raw materials within the above composition range, and after melting, solidified by casting or the like to produce a base material.
母材には、まず、４６０℃以下、４時間以上の条件で均質化処理を施す。この均質化処理により、鋳造時に形成されるデンドライド組織の少ないマグネシウム相と準結晶粒子相とが形成する。温度が４６０℃を超えると、準結晶粒子相がマグネシウム母相に溶解し、所期の効果が得られない。また、４時間未満であると、均質化処理が不十分であるため、鋳造組織が残る。 The base material is first subjected to a homogenization treatment under conditions of 460 ° C. or lower and 4 hours or longer. By this homogenization treatment, a magnesium phase and a quasicrystalline particle phase having a small dendride structure formed during casting are formed. When the temperature exceeds 460 ° C., the quasicrystalline particle phase dissolves in the magnesium matrix and the desired effect cannot be obtained. If it is less than 4 hours, the cast structure remains because the homogenization treatment is insufficient.
均質化処理後には焼入れを行うことができる。焼入れによって組織を一旦凍結させることができ、組織の安定化を図ることができる。 Quenching can be performed after the homogenization treatment. The tissue can be frozen once by quenching, and the tissue can be stabilized.
次いで、ひずみ加工後にマグネシウム母相の大きさが５μｍ以下になる温度で、母材全体がその温度に行き渡るのに要する時間保持する。熱処理温度は、ひずみ加工時の温度と同等である。熱処理温度がひずみ加工温度より高いと、平均結晶粒径５μｍ以下の微細なマグネシウム母相が形成されず、ひずみ加工温度より低いと、加工中に割れ等が発生し、健全な押出し材を得ることができない。熱処理を行わない場合にも、ひずみ加工中に割れ等が発生し、健全な押出し材を得ることができない。熱処理時間は、１５分間〜９０分間を一応の目安とすることができる。 Next, at a temperature at which the size of the magnesium matrix becomes 5 μm or less after strain processing, the time required for the entire matrix to reach the temperature is maintained. The heat treatment temperature is equivalent to the temperature during strain processing. When the heat treatment temperature is higher than the strain processing temperature, a fine magnesium matrix having an average crystal grain size of 5 μm or less is not formed. When the heat treatment temperature is lower than the strain processing temperature, cracks and the like are generated during processing to obtain a sound extruded material. I can't. Even when heat treatment is not performed, cracks and the like occur during strain processing, and a sound extruded material cannot be obtained. The heat treatment time can be set as a rough standard for 15 minutes to 90 minutes.
そして、上記熱処理と同温度の温間温度以上で８：１以上のひずみ加工を施す。ひずみ加工は、圧延、押出し、鍛造等により行うことができる。加えられるひずみにより、再結晶が起こり、平均結晶粒径が５μｍ以下の微細なマグネシウム母相が形成されるとともに、転位が導入されて、母相結晶粒内に平均粒子径０．２μｍ以下の準結晶粒子相が形成され、準結晶粒子相が整合な界面を持ってマグネシウム母相に均一に分散する。加工比が８：１未満では、加えられるひずみが不十分であり、平均結晶粒径が５μｍ以下の微細なマグネシウム母相が形成されず、また、導入される転位の密度が低く、準結晶粒子相の均一な分散が得られない。 And strain processing of 8: 1 or more is performed at a temperature equal to or higher than the temperature of the heat treatment. Strain processing can be performed by rolling, extruding, forging, or the like. Due to the applied strain, recrystallization occurs, and a fine magnesium matrix having an average crystal grain size of 5 μm or less is formed, and dislocations are introduced, and a quasi-crystal having an average grain diameter of 0.2 μm or less is introduced into the matrix crystal grains. A crystal grain phase is formed, and the quasi-crystal grain phase is uniformly dispersed in the magnesium matrix with a consistent interface. If the processing ratio is less than 8: 1, the applied strain is insufficient, a fine magnesium matrix having an average crystal grain size of 5 μm or less is not formed, and the density of dislocations introduced is low, so A uniform dispersion of the phases cannot be obtained.
このように、本発明のマグネシウム合金展伸材の製造方法は、均質化処理−熱処理−温間温度域でのひずみ加工という実用化技術に適した簡略化された工程からなる。高強度で高延性を有するとともに、圧縮強度および破壊靱性が高いマグネシウム合金展伸材を簡便に製造することができる。 Thus, the manufacturing method of the magnesium alloy extended material of this invention consists of the simplified process suitable for the practical use technique of homogenization process-heat processing-strain processing in a warm temperature range. A magnesium alloy wrought material having high strength and high ductility and high compressive strength and high fracture toughness can be easily produced.
なお、前記の準結晶粒子相の平均粒子径とマグネシウム母相の平均結晶粒径との比ＫＢを０．０１以上０．２以下とするためには、ひずみ加工における加工温度とひずみ量とを制御すればよい。Incidentally, the ratio K B between the average mean crystal grain size of the particle diameter and the magnesium mother phase of the quasi-crystalline particle phase to 0.01 to 0.2 has a processing temperature in the strain work strain amount and Can be controlled.
以下の実施例においての合金組織についての結晶粒や粒子の平均径は、市販の画像ソフトウェア(PhotoShop：登録商標)を使用し、コントラストの強いところ（黒色の箇所）を粒子とみなし、２５０点以上の結晶粒、粒子について測定してその平均値を求めたものである。 In the following examples, the average diameter of the crystal grains and particles for the alloy structure is 250 or more, using a commercially available image software (PhotoShop: registered trademark), considering a strong contrast (black part) as a particle. The crystal grains and particles were measured and the average value was obtained.
また、引張り・圧縮強度については、応力−ひずみ曲線から求めている。具体的には、ひずみ０．２％の値の応力値を測定している。 The tensile / compressive strength is obtained from a stress-strain curve. Specifically, the stress value with a strain of 0.2% is measured.
伸びについては、破断後の試験片をつなぎ合わせ、もとの長さから求めている。平面ひずみ破壊靱性試験についてはＡＳＴＭ−Ｅ３９９に準拠している。
＜１＞ＺＫ６０組成のマグネシウム合金
商業用マグネシウム合金（Ｍｇ−６ｗｔ．％Ｚｎ−０．５ｗｔ．％Ｚｒ：材料名ＺＫ６０）に球状粒子を析出させた例である。
（実験Ｎｏ．１）
ＺＫ６０に、５００℃にて２時間炉中保持し、均質化処理を行った。炉から取出した後、水焼き入れを行うことで、組織を凍結した。The elongation is obtained from the original length by joining the test pieces after fracture. The plane strain fracture toughness test conforms to ASTM-E399.
<1> Magnesium alloy with ZK60 composition This is an example in which spherical particles are precipitated on a commercial magnesium alloy (Mg-6 wt.% Zn-0.5 wt.% Zr: material name ZK60).
(Experiment No. 1)
ZK60 was kept in a furnace at 500 ° C. for 2 hours for homogenization. After removal from the furnace, the tissue was frozen by water quenching.
その後、機械加工により、押出しビレットを作成した。次いで、ビレットを３８０℃に昇温させた後０．５時間程度保持し、１８：１の押出し比で押出し加工を施し、押出し材を得た。 Then, the extrusion billet was created by machining. Next, the billet was heated to 380 ° C. and held for about 0.5 hour, and extrusion was performed at an extrusion ratio of 18: 1 to obtain an extruded material.
組織観察の結果（図１参照）、表１にも示したように、マグネシウム母相の平均結晶粒径は１３．５μｍ程度で、３５〜５０ｎｍの平均粒子径の第二相の球状析出粒子の組織を示すことが確認された。 As a result of the structure observation (see FIG. 1), as shown in Table 1, the average crystal grain size of the magnesium matrix is about 13.5 μm, and the second phase spherical precipitated particles having an average particle size of 35 to 50 nm. Confirmed to represent the organization.
第二相粒子の最大体積率は約５％に至り、その心心間隔は１００〜２００ｎｍであった。
（実験Ｎｏ．２：比較例）
商業用マグネシウム合金（Ｍｇ−６ｗｔ．％Ｚｎ−０．５ｗｔ．％Ｚｒ：ＺＫ６０）に５００℃にて２時間炉中保持し、均質化処理を行った。炉から取出した後、水焼き入れを行うことで、組織を凍結した。その後、機械加工により押出しビレットを作成した。ビレットを３８０℃に昇温させた後、０．５時間程度保持し、１８：１の押出し比で押出し加工を施し、押出し材を得た。押出し材をさらに３６０℃にて２４時間均質化処理後、水焼き入れを行い、１７５℃、１×１０５秒で時効処理を施した。The maximum volume fraction of the second phase particles reached about 5%, and the center-to-center distance was 100 to 200 nm.
(Experiment No. 2: Comparative Example)
A commercial magnesium alloy (Mg-6 wt.% Zn-0.5 wt.% Zr: ZK60) was held in a furnace at 500 ° C. for 2 hours for homogenization. After removal from the furnace, the tissue was frozen by water quenching. Thereafter, an extruded billet was prepared by machining. After raising the temperature of the billet to 380 ° C., the billet was held for about 0.5 hour and subjected to extrusion at an extrusion ratio of 18: 1 to obtain an extruded material. The extruded material was further homogenized at 360 ° C. for 24 hours, and then quenched with water and subjected to aging at 175 ° C. and 1 × 10 5 seconds.
組織観察の結果（図２参照）、表１にも示したように、平均結晶粒径は１３．５μｍ程度で、約７５ｎｍ程度の針状析出粒子が確認され、結晶粒径は同じであるが、析出粒子形態の異なる試料を作成することができた。
（特性の対比）
上記の各々の試料についての破断伸び、降伏強度、平面ひずみ破壊靱性値の測定結果を表１に示した。As a result of the structure observation (see FIG. 2), as shown in Table 1, the average crystal grain size is about 13.5 μm, and needle-like precipitated particles of about 75 nm are confirmed, and the crystal grain size is the same. Samples with different precipitated particle morphology could be prepared.
(Characteristic contrast)
Table 1 shows the measurement results of elongation at break, yield strength, and plane strain fracture toughness for each of the above samples.
なお、平面ひずみ破壊靱性値については、それぞれの試料から破壊靱性試験片を採取し、ストレッチゾーン破面解析より求めた。すなわち、それぞれの押出し材から、ＡＳＴＥ−Ｅ３９９に準拠した５×１０×４０ｍｍの形状を有する三点曲げ破壊靱性試験片を採取し、ストレッチゾーン破面解析により、平面ひずみ破壊靱性値を求めた。 In addition, about the plane strain fracture toughness value, the fracture toughness test piece was extract | collected from each sample, and it calculated | required from the stretch zone fracture surface analysis. That is, a three-point bending fracture toughness test piece having a shape of 5 × 10 × 40 mm based on ASTE-E399 was collected from each extruded material, and a plane strain fracture toughness value was obtained by stretch zone fracture surface analysis.
それぞれ、２２．４および２１．０ＭＰａｍ１／２と求まり、球状析出粒子を有する実験Ｎｏ．１の試料の方が高い平面ひずみ破壊靱性値を示した。
＜２＞Ｍｇ−Ｚｎ二元系マグネシウム合金
（球状析出粒子の形成）
商用純マグネシウム（純度９９．９５％）に、２．４原子％亜鉛を溶解鋳造し、母合金（材料名Ｍｇ−２．４Ｚｎ）を準備した。Experiment No. 2 with spherical precipitate particles, which were found to be 22.4 and 21.0 MPam 1/2 , respectively. Sample 1 showed a higher plane strain fracture toughness value.
<2> Mg-Zn binary magnesium alloy (formation of spherical precipitated particles)
2.4 atomic% zinc was melt cast in commercial pure magnesium (purity 99.95%) to prepare a master alloy (material name: Mg-2.4Zn).
この母合金を３００℃以上にて４８時間炉中保持し、均質化処理を行った。炉から取り出した後、水焼入れを行うことで、組織を凍結した。その後、機械加工により、押出しビレットを作成した。 This mother alloy was held in a furnace at 300 ° C. or higher for 48 hours, and homogenized. After removal from the furnace, the tissue was frozen by water quenching. Then, the extrusion billet was created by machining.
次いでビレットを約２１０℃に昇温させた後０．５時間程度保持し、約２０：１の押出し比で押出し加工を施し、押出し材を得た。 Next, the billet was heated to about 210 ° C. and held for about 0.5 hours, and extrusion was performed at an extrusion ratio of about 20: 1 to obtain an extruded material.
透過型電子顕微鏡（ＴＥＭ）組織観察の結果、押出し過程の完了した部位（図３参照）では第二相球状析出粒子の存在が確認された。また、押出し途中の部位（図４参照）では針状形態の混在した析出粒子が確認された。 As a result of observation with a transmission electron microscope (TEM), the presence of second-phase spherical precipitated particles was confirmed at the site where the extrusion process was completed (see FIG. 3). Moreover, the precipitation particle | grains with which the acicular form was mixed were confirmed in the site | part (refer FIG. 4) in the middle of extrusion.
図３より、マグネシウム母相（図中のコントラストの濃い部分）の平均結晶粒径（ｄ）は約１μｍを示し、また、マグネシウム母相に平均粒子系０．１μｍ程度の球状析出物（矢印で示す）の形成が確認できる。 From FIG. 3, the average crystal grain size (d) of the magnesium matrix (the dark portion in the figure) is about 1 μm, and spherical precipitates with an average particle size of about 0.1 μm (as indicated by arrows) in the magnesium matrix. Formation) can be confirmed.
鋳造マグネシウム合金に押出し等のひずみ加工を導入することにより、球状析出粒子を形成することがわかる。
（実験Ｎｏ．３〜１０）
商用純マグネシウム（純度９９．９５％）に、１．９、２．４、３．０または３．４原子％亜鉛を溶解鋳造し、母合金（材料名Ｍｇ−１．９Ｚｎ、Ｍｇ−２．４Ｚｎ、Ｍｇ−３．０Ｚｎ、Ｍｇ−３．４Ｚｎ）を準備した。It can be seen that spherical precipitated particles are formed by introducing strain processing such as extrusion into the cast magnesium alloy.
(Experiment No. 3 to 10)
1.9, 2.4, 3.0, or 3.4 atomic% zinc is melt-cast in commercial pure magnesium (purity 99.95%), and the master alloys (material names Mg-1.9Zn, Mg-2. 4Zn, Mg-3.0Zn, Mg-3.4Zn) were prepared.
表１に示すように、母合金を種々の温度（３００℃〜４００℃）にて２４〜４８時間炉中保持し、均質化処理を行った。炉から取出した後、水焼き入れを行うことで、組織を凍結した。 As shown in Table 1, the master alloy was held in a furnace at various temperatures (300 ° C. to 400 ° C.) for 24 to 48 hours, and homogenized. After removal from the furnace, the tissue was frozen by water quenching.
その後、機械加工により、押出ビレットを作成した。次いで、ビレットを種々の温度（２００〜２３０℃）に昇温させた後０．５時間程度保持し、１８：１の押出し比で押出し加工を施し、押出し材を得た。 Then, the extrusion billet was created by machining. Next, after raising the billet to various temperatures (200 to 230 ° C.), the billet was held for about 0.5 hour and extruded at an extrusion ratio of 18: 1 to obtain an extruded material.
ＴＥＭを用いた全てのＭｇ−Ｘａｔ．％Ｚｎ（Ｘ＝１．９，２．４，３．０，３．４）押出し材の平均結晶粒径と析出粒子径の関係も表１にまとめる。 All Mg-Xat. Table 1 also summarizes the relationship between the average crystal grain size and the precipitated particle size of the% Zn (X = 1.9, 2.4, 3.0, 3.4) extruded material.
また、それぞれの押出し材から、ＡＳＴＥ−Ｅ３９９に準拠した５×１０×４０ｍｍの形状を有する三点曲げ破壊靱性試験片を採取し、ストレッチゾーン破面解析により、平面ひずみ破壊靱性値を求めた。そして、押出し材から平行部ｆ２．５×１０ｍｍを有する試験片を採取し、引張り試験を行った。 In addition, a three-point bending fracture toughness test piece having a shape of 5 × 10 × 40 mm based on ASTE-E399 was taken from each extruded material, and a plane strain fracture toughness value was obtained by stretch zone fracture surface analysis. And the test piece which has parallel part f2.5 * 10mm from the extruded material was extract | collected, and the tension test was done.
典型的なストレッチゾーン破面解析のＳＥＭ観察結果を実験Ｎｏ．５の場合について図５に、破壊靱性試験ならびに引張り試験の結果を表１に示した。
＜３＞ＺＫ６０組成合金の平面ひずみ破壊靱性値
（実験Ｎｏ．１１〜１２）
商業用マグネシウム合金（Ｍｇ−６ｗｔ．％Ｚｎ−０．５ｗｔ．％Ｚｒ：材料名ＺＫ６０）に、５００℃にて２時間炉中保持し、均質化処理を行った。炉から取出した後、水焼き入れを行うことで、組織を凍結した。SEM observation results of typical stretch zone fracture surface analysis are shown in Experiment No. The results of the fracture toughness test and the tensile test are shown in FIG.
<3> Plane strain fracture toughness value of ZK60 composition alloy (Experiment Nos. 11 to 12)
A commercial magnesium alloy (Mg-6 wt.% Zn-0.5 wt.% Zr: material name ZK60) was held in a furnace at 500 ° C. for 2 hours for homogenization. After removal from the furnace, the tissue was frozen by water quenching.
その後、機械加工により、押出しビレットを作成した。次いで、ビレットを２００℃（実験Ｎｏ．１１）および２２０℃（実験Ｎｏ．１２）に昇温させた後０．５時間程度保持し、１８：１の押出し比で押出し加工を施し、押出し材を得た。 Then, the extrusion billet was created by machining. Next, the billet was heated to 200 ° C. (Experiment No. 11) and 220 ° C. (Experiment No. 12) and then held for about 0.5 hour, subjected to extrusion at an extrusion ratio of 18: 1, and the extruded material was Obtained.
ＴＥＭ組織観察の結果を図６（実験Ｎｏ．１１）および図７（実験Ｎｏ．１２）に示した。 The results of TEM structure observation are shown in FIG. 6 (Experiment No. 11) and FIG. 7 (Experiment No. 12).
２２０℃押出し材（実験Ｎｏ．１２）の場合、表１に示したように、組織観察の結果、母相の平均結晶粒径は１．５μｍ程度で、２５〜５０ｎｍ程度の均一微細分散した球状な第二相析出粒子の組織を示すことが確認された。一方、２００℃押出し材：実験Ｎｏ．１１では、母相の平均結晶粒径は０．５μｍ程度であった。押出し材から引張試験片ならびに破壊靱性試験片を採取し、それぞれ試験を行った。 In the case of the 220 ° C. extruded material (Experiment No. 12), as shown in Table 1, as a result of the structure observation, the average crystal grain size of the parent phase was about 1.5 μm, and the uniform finely dispersed spherical shape of about 25 to 50 nm. It was confirmed that the structure of the second phase precipitated particles was shown. On the other hand, extruded material at 200 ° C .: Experiment No. In No. 11, the average crystal grain size of the mother phase was about 0.5 μm. Tensile test pieces and fracture toughness test pieces were sampled from the extruded materials and tested.
２２０℃押出し材：実験Ｎｏ．１２の引張試験の結果、引張降伏強度２８６ＭＰａ、破断伸び２７％の高強度・高延性が確認された。また、破壊靱性試験の結果より、平面ひずみ破壊靱性値は３４．８ＭＰａｍ１／２と求まり、温間温度域でひずみ加工を導入することにより高靱性を達成することができた。Extruded material at 220 ° C .: Experiment No. As a result of the tensile test of No. 12, high strength and high ductility with a tensile yield strength of 286 MPa and a breaking elongation of 27% were confirmed. Further, from the results of the fracture toughness test, the plane strain fracture toughness value was found to be 34.8 MPam 1/2, and high toughness could be achieved by introducing strain processing in the warm temperature range.
なお、図８には、このマグネシウム合金とその比較例としての一般的な商用マグネシウム合金(Cast Mg, wrough Mg)並びにアルミニウム合金(J. R. Davis, Aluminum and Aluminum Alloys, ASM Specialty Handbook, ASM International, Materials Park, OH, 1993) の靱性と比強度の関係を示した。 FIG. 8 shows this magnesium alloy, a general commercial magnesium alloy (Cast Mg, wrough Mg) and an aluminum alloy (JR Davis, Aluminum and Aluminum Alloys, ASM Specialty Handbook, ASM International, Materials Park) as a comparative example. , OH, 1993) showed the relationship between toughness and specific strength.
本発明マグネシウム合金は、商用高強度アルミニウム合金と同程度の強度−靱性特性を有することがわかる。
＜４＞Ｍｇ−１．８ａｔ．％Ｚｎ−０．３ａｔ．％Ｃａ合金とその平面ひずみ破壊靱性値
（実験Ｎｏ．１３）
商用純マグネシウム（純度９９．９５％）に、１．８原子％亜鉛と０．３原子％カルシウムを溶解鋳造し、母合金を準備した。次いで、母合金を５００℃にて２時間炉中保存し、均質化処理を行った。炉から取出した後、水焼き入れを行うことで、組織を凍結した。
その後、機械加工により、押出しビレットを作成した。このビレットを約２５０℃に昇温させた後０．５時間程度保持し、約１８：１の押出し比で押出し加工を施し、押出し材を得た。It can be seen that the magnesium alloy of the present invention has the same strength-toughness characteristics as commercial high-strength aluminum alloys.
<4> Mg-1.8 at. % Zn-0.3 at. % Ca alloy and its plane strain fracture toughness (Experiment No. 13)
1.8 atomic% zinc and 0.3 atomic% calcium were melt cast in commercial pure magnesium (purity 99.95%) to prepare a master alloy. Subsequently, the mother alloy was stored in a furnace at 500 ° C. for 2 hours, and homogenized. After removal from the furnace, the tissue was frozen by water quenching.
Then, the extrusion billet was created by machining. The billet was heated to about 250 ° C. and held for about 0.5 hour, and extrusion was performed at an extrusion ratio of about 18: 1 to obtain an extruded material.
組織観察の結果、表１に示したように、マグネシウム母相の平均結晶粒径は１μｍ程度で２５〜５０ｎｍ程度の均一微細分散した球状な析出粒子が確認された。 As a result of the structure observation, as shown in Table 1, it was confirmed that the average crystal grain size of the magnesium matrix was about 1 μm, and spherical precipitated particles having a uniform fine dispersion of about 25 to 50 nm were confirmed.
押出し材から引張試験片ならびに破壊靱性試験片を採取し、それぞれ試験を行った。 Tensile test pieces and fracture toughness test pieces were sampled from the extruded materials and tested.
表１に示したように、引張試験の結果、引張降伏強度３１０ＭＰａ、破断伸び１６％の高強度・高延性が確認された。 As shown in Table 1, as a result of the tensile test, high strength and high ductility with a tensile yield strength of 310 MPa and a breaking elongation of 16% were confirmed.
また、破壊靱性試験の結果より、平面ひずみ破壊靱性値は２８．１ＭＰａｍ１／２と求まり、マグネシウム合金鋳造材を温間温度域でひずみ加工を導入することにより高強度・高靱性を達成することができた。Also, from the results of the fracture toughness test, the plane strain fracture toughness value is 28.1 MPam 1/2, and high strength and high toughness are achieved by introducing strain processing of the magnesium alloy cast material in the warm temperature range. I was able to.
＜５＞Ｍｇ−６ａｔ．％Ｚｎ−１ａｔ．％Ｈｏ合金
（実験Ｎｏ．１４−１５）
商用純マグネシウム（Ｍｇ、純度９９．９５％）に、６原子％の亜鉛（Ｚｎ）および１原子％のホロニウム（Ｈｏ）を常法に従い溶解し、鋳造してインゴットを作製した。インゴットを４００℃で２４時間炉中に保持し、均質化処理を行った。炉から取り出し、水焼入れを行い、組織を凍結した。その後、機械加工によりφ４０×５０ｍｍの押出しビレットを作製した。<5> Mg-6 at. % Zn-1 at. % Ho alloy (Experiment No. 14-15)
6 atomic% zinc (Zn) and 1 atomic% holonium (Ho) were dissolved in commercial pure magnesium (Mg, purity 99.95%) according to a conventional method, and cast to prepare an ingot. The ingot was held in a furnace at 400 ° C. for 24 hours, and homogenized. The tissue was removed from the furnace and water quenched. Thereafter, an extruded billet of φ40 × 50 mm was produced by machining.
押出しビレットを２３０℃（５０３Ｋ）：実験Ｎｏ．１４または３００℃（５７３Ｋ）：実験Ｎｏ．１５に昇温させた後、３０分間保持し、その後、同温度において押出し比２５：１の押出しを施し、φ８×１０００ｍｍ超の押出し材を得た。 Extrude billet at 230 ° C. (503 K): Experiment No. 14 or 300 ° C. (573 K): Experiment No. After raising the temperature to 15, the mixture was held for 30 minutes, and then extruded at an extrusion ratio of 25: 1 at the same temperature to obtain an extruded material having a diameter of more than φ8 × 1000 mm.
２３０℃（５０３Ｋ）：実験Ｎｏ．１４で押出しを施した押出し材について、透過型電子顕微鏡（ＴＥＭ）を用いて組織観察を行った。図９に示したように、平均結晶粒径ｄが１．５μｍ程度のマグネシウム母相に平均粒子径が０．１μｍの準結晶相（図中に白矢印で示した部分）が均一に分散した組織が形成されていることが確認された。前述の式で求められる準結晶粒子相の平均粒子径とマグネシウム母相の平均結晶粒径との比ＫＢは、０．０７であった。230 ° C. (503 K): Experiment No. About the extruded material which performed extrusion by 14, the structure | tissue observation was performed using the transmission electron microscope (TEM). As shown in FIG. 9, the quasicrystalline phase (the portion indicated by the white arrow in the figure) having an average particle size of 0.1 μm was uniformly dispersed in the magnesium matrix having an average crystal particle size d of about 1.5 μm. It was confirmed that an organization was formed. The ratio K B between the average mean crystal grain size of the particle diameter and the magnesium mother phase of the quasi-crystalline particle phase obtained by the formula described above, was 0.07.
押出し材から平行部φ３×１５ｍｍを有する引張試験片およびφ４×８ｍｍの圧縮試験片を採取し、室温において引張試験および圧縮試験を行った。引張試験には万能試験機を用い、ひずみ速度１０−３ｓ−１で行った。圧縮試験には万能試験機を用い、同様にひずみ速度１×１０−３ｓ−１で行った。A tensile test piece having a parallel part φ3 × 15 mm and a compression test piece of φ4 × 8 mm were taken from the extruded material, and a tensile test and a compression test were performed at room temperature. The tensile test was performed at a strain rate of 10 −3 s −1 using a universal testing machine. A universal testing machine was used for the compression test and was similarly performed at a strain rate of 1 × 10 −3 s −1 .
引張試験および圧縮試験の結果は表２に示した通りである。表２には、押出し温度、マグネシウム母相の平均結晶粒径および準結晶粒子相の平均粒子径を併せて示した。 The results of the tensile test and the compression test are as shown in Table 2. Table 2 also shows the extrusion temperature, the average crystal grain size of the magnesium matrix, and the average grain size of the quasicrystalline particle phase.
２３０℃（５０３Ｋ）で押出しを施した試料（実験Ｎｏ．１４）については、引張降伏強度２８０ＭＰａ、破断伸び１６％の高強度・高延性が確認された。また、圧縮降伏強度３００ＭＰａが確認され、圧縮強度/引張強度の比は１．０６であり、引張強度と同等の圧縮強度を示すことが確認された。高強度で高延性を有するとともに、圧縮強度の高いマグネシウム合金であることがわかる。 The sample (experiment No. 14) extruded at 230 ° C. (503 K) was confirmed to have high strength and high ductility with a tensile yield strength of 280 MPa and a breaking elongation of 16%. Further, a compressive yield strength of 300 MPa was confirmed, and the ratio of compressive strength / tensile strength was 1.06, and it was confirmed that the compressive yield strength was equivalent to the tensile strength. It can be seen that it is a magnesium alloy having high strength and high ductility and high compressive strength.
３００℃（５７３Ｋ）で押出しを施した試料（実験Ｎｏ．１５）については、表２に示したように、マグネシウム母相の平均結晶粒径が３μｍ程度、準結晶粒子相の平均粒子径が０．２μｍであり、２３０℃（５０３Ｋ）（実験Ｎｏ．１４）で押出しを施した試料に比べわずかに大きい。また、表２に示したように、引張強度２６５ＭＰａ、破断伸び１３％および圧縮強度２４８ＭＰａが確認された。高強度で高延性を有するとともに、圧縮強度の高いマグネシウム合金展伸材であることがわかる。一方、２３０℃（５０３Ｋ）（実験Ｎｏ．１４）で押出しを施した試料と比較すると、圧縮強度/引張強度の比は０．９４であり、熱処理温度および押出し温度の上昇にともない、圧縮強度が若干低下することが分かる。
＜６＞Ｍｇ−２．７ａｔ．％Ｚｎ−０．４ａｔ．％Ｈｏ合金
（実験Ｎｏ．１６−１８）
商用純マグネシウム（Ｍｇ、純度９９．９５％）に、２．７原子％の亜鉛（Ｚｎ）および０．４原子％のホロニウム（Ｈｏ）を常法に従い溶解し、鋳造してインゴットを作製した。インゴットを４００℃で２４時間炉中に保持し、均質化処理を行った。炉から取り出し、水焼入れを行い、組織を凍結した。その後、機械加工によりφ４０×５０ｍｍの押出しビレットを作製した。As shown in Table 2, for the sample extruded at 300 ° C. (573 K) (Experiment No. 15), the average crystal grain size of the magnesium matrix was about 3 μm, and the average grain size of the quasicrystalline particle phase was 0. 2 μm, slightly larger than the sample extruded at 230 ° C. (503 K) (Experiment No. 14). Further, as shown in Table 2, a tensile strength of 265 MPa, a breaking elongation of 13% and a compressive strength of 248 MPa were confirmed. It can be seen that this is a magnesium alloy wrought material having high strength and high ductility and high compressive strength. On the other hand, compared with the sample extruded at 230 ° C. (503 K) (Experiment No. 14), the ratio of compressive strength / tensile strength is 0.94, and as the heat treatment temperature and the extrusion temperature increase, the compressive strength increases. It turns out that it falls a little.
<6> Mg-2.7 at. % Zn-0.4 at. % Ho alloy (Experiment No. 16-18)
In commercial pure magnesium (Mg, purity 99.95%), 2.7 atomic% of zinc (Zn) and 0.4 atomic% of holonium (Ho) were dissolved according to a conventional method and cast to prepare an ingot. The ingot was held in a furnace at 400 ° C. for 24 hours, and homogenized. The tissue was removed from the furnace and water quenched. Thereafter, an extruded billet of φ40 × 50 mm was produced by machining.
押出しビレットを２１０℃（４８３Ｋ）（実験Ｎｏ．１６）、２６０℃（５３３Ｋ）（実験Ｎｏ．１７）または３００℃（５７３Ｋ）（実験Ｎｏ．１８：比較例）に昇温させた後、３０分間保持し、その後、同温度において押出し比１８：１、あるいは２５：１での押出し加工を施し、φ８×１０００ｍｍ超の押出し材を得た。 30 minutes after raising the temperature of the extruded billet to 210 ° C. (483 K) (Experiment No. 16), 260 ° C. (533 K) (Experiment No. 17) or 300 ° C. (573 K) (Experiment No. 18: Comparative Example) After that, extrusion was performed at the same temperature at an extrusion ratio of 18: 1 or 25: 1 to obtain an extruded material having a diameter of more than φ8 × 1000 mm.
２１０℃（４８３Ｋ）（実験Ｎｏ．１６）で押出しを施した押出し材について、透過型電子顕微鏡（ＴＥＭ）を用いて組織観察を行った。図１０（ａ）に示したように平均結晶粒径が１μｍ程度のマグネシウム母相（図中のコントラストの濃い部分）に、図１０（ｂ）に示したように平均粒子径が０．１μｍの準結晶が均一に分散した組織が形成されていることが確認された。ＫＢ値は０．１であった。また、図１０（ｂ）図中に示した白枠内を高分解能ＴＥＭを用いて観察した。その結果、図１０（ｃ）に示したように、マグネシウム母相と準結晶粒子相との界面は９０％以上整合していることが確認された。About the extruded material which extruded at 210 degreeC (483K) (experiment No. 16), structure | tissue observation was performed using the transmission electron microscope (TEM). As shown in FIG. 10 (a), the average grain size is about 1 μm in the magnesium matrix (the dark portion in the figure), and the average grain size is 0.1 μm as shown in FIG. 10 (b). It was confirmed that a structure in which the quasicrystal was uniformly dispersed was formed. K B value was 0.1. Further, the inside of the white frame shown in FIG. 10B was observed using a high resolution TEM. As a result, as shown in FIG. 10 (c), it was confirmed that the interface between the magnesium matrix phase and the quasicrystalline particle phase matched 90% or more.
押出し材から上記Ｍｇ−６ａｔ．％Ｚｎ−１ａｔ．％Ｈｏ合金と同様な引張試験片および圧縮試験片を採取し、室温において引張試験および圧縮試験を行った。 From the extruded material, the above Mg-6 at. % Zn-1 at. Tensile test pieces and compression test pieces similar to the% Ho alloy were sampled and subjected to tensile tests and compression tests at room temperature.
引張試験および圧縮試験の結果を表２に併せて示した。 Table 2 shows the results of the tensile test and the compression test.
２１０℃（４８３Ｋ）：実験Ｎｏ．１６で押出しを施した試料については、引張降伏強度３０４ＭＰａ、破断伸び１８％の高強度・高延性が確認された。また、圧縮降伏強度２９０ＭＰａが確認され、圧縮強度/引張強度の比は０．９５であり、引張強度と同等の圧縮強度を示すことが確認された。高強度で高延性を有するとともに、圧縮強度の高いマグネシウム合金であることがわかる。 210 ° C. (483 K): Experiment No. The sample extruded at 16 was confirmed to have high strength and high ductility with a tensile yield strength of 304 MPa and a breaking elongation of 18%. Further, a compressive yield strength of 290 MPa was confirmed, and the ratio of compressive strength / tensile strength was 0.95, confirming that compressive strength equivalent to the tensile strength was exhibited. It can be seen that it is a magnesium alloy having high strength and high ductility and high compressive strength.
２６０℃（５３３Ｋ）：実験Ｎｏ．１７、３００℃（５７３Ｋ）：実験Ｎｏ．１８でそれぞれ押出しを施した試料についての組織観察結果ならびに引張試験および圧縮試験結果も表２に併せて示した。 260 ° C. (533 K): Experiment No. 17, 300 ° C. (573 K): Experiment No. Table 2 also shows the structure observation results and the tensile test and compression test results for the samples extruded at 18 respectively.
押出し温度の上昇にともなってマグネシウム母相の平均結晶粒径および準結晶粒子相の平均粒子径が大きくなり、圧縮強度が低下する傾向にあることがわかる。３００℃（５７３Ｋ）：実験Ｎｏ．１８で押出しを施した試料では、マグネシウム母相の平均結晶粒径が１５μｍ程度となり、本発明のマグネシウム合金には実質的に該当しない。この試料の圧縮強度/引張強度の比が０．７６と低い。熱処理温度および押出し温度が高かったためと推定される。 It can be seen that as the extrusion temperature rises, the average grain size of the magnesium matrix and the average grain size of the quasicrystalline grain phase increase, and the compressive strength tends to decrease. 300 ° C. (573 K): Experiment No. In the sample extruded at 18, the average crystal grain size of the magnesium matrix is about 15 μm, and does not substantially correspond to the magnesium alloy of the present invention. The compression strength / tensile strength ratio of this sample is as low as 0.76. It is estimated that the heat treatment temperature and the extrusion temperature were high.
次に、平面ひずみ破壊靱性値を求めた。 Next, the plane strain fracture toughness value was determined.
実験Ｎｏ．１６の押出し材から５×１０×４０ｍｍの三点曲げ破壊靱性試験片を採取し、万能試験機を用い、ＡＳＴＭ−Ｅ３９９に規定されている条件で破壊靱性試験を行った。図１１は、破壊靱性試験後の破面を走査型電子顕微鏡（ＳＥＭ）を用いて観察した像である。そして、破壊靭性後の破面を用いたストレッチゾーン解析により平面ひずみ破壊靱性値を求めた。平面ひずみ破壊靱性値は３２．１ＭＰａ・ｍ１/２であり、高靱性が確認された。
＜７＞Ｍｇ−２．６ａｔ．％Ｚｎ−０．４ａｔ．％Ｙ合金展
（実験Ｎｏ．１９）
商用純マグネシウム（Ｍｇ、純度９９．９５％）に、２．６原子％の亜鉛（Ｚｎ）および０．４原子％のイットリウム（Ｙ）を常法に従い溶解し、鋳造してインゴットを作製した。インゴットを４００℃で２４時間炉中に保持し、均質化処理を行った。炉から取り出し、水焼入れを行い、組織を凍結した。その後、機械加工によりφ４０×５０ｍｍの押出しビレットを作製した。Experiment No. A 5 × 10 × 40 mm three-point bending fracture toughness test piece was sampled from 16 extruded materials, and a fracture toughness test was performed under the conditions specified in ASTM-E399 using a universal testing machine. FIG. 11 is an image obtained by observing the fracture surface after the fracture toughness test using a scanning electron microscope (SEM). And the plane strain fracture toughness value was calculated | required by the stretch zone analysis using the fracture surface after fracture toughness. The plane strain fracture toughness value was 32.1 MPa · m 1/2 , confirming high toughness.
<7> Mg-2.6 at. % Zn-0.4 at. % Y Alloy Exhibition (Experiment No. 19)
2.6 atomic% zinc (Zn) and 0.4 atomic% yttrium (Y) were dissolved in commercial pure magnesium (Mg, purity 99.95%) according to a conventional method, and cast to prepare an ingot. The ingot was held in a furnace at 400 ° C. for 24 hours, and homogenized. The tissue was removed from the furnace and water quenched. Thereafter, an extruded billet of φ40 × 50 mm was produced by machining.
押出しビレットを２１０℃（４８３Ｋ）に昇温させた後、３０分間保持し、その後、同温度において押出し比１８：１の押出し加工を施し、φ８×１０００ｍｍ超の押出し材を得た。 After raising the temperature of the extruded billet to 210 ° C. (483 K), the extruded billet was held for 30 minutes, and then extruded at an extrusion ratio of 18: 1 at the same temperature to obtain an extruded material having a diameter of more than φ8 × 1000 mm.
透過型電子顕微鏡（ＴＥＭ）を用いて組織観察を行った。平均結晶粒径が１μｍ程度のマグネシウム母相に平均粒子径が０．１μｍの準結晶が均一に分散した組織が形成されていることが確認された。ＫＢ値は０．１であった。The structure was observed using a transmission electron microscope (TEM). It was confirmed that a structure in which quasicrystals having an average particle size of 0.1 μm were uniformly dispersed was formed in a magnesium matrix having an average crystal size of about 1 μm. K B value was 0.1.
押出し材から上記Ｍｇ−６ａｔ．％Ｚｎ−１ａｔ．％Ｈｏ合金と同様な引張試験片および圧縮試験片を採取し、室温において引張試験および圧縮試験を行った。試験条件も上記Ｍｇ−６ａｔ．％Ｚｎ−１ａｔ．％Ｈｏ合金展伸材についての試験条件と同じにした。 From the extruded material, the above Mg-6 at. % Zn-1 at. Tensile test pieces and compression test pieces similar to the% Ho alloy were sampled and subjected to tensile tests and compression tests at room temperature. The test conditions were also Mg-6 at. % Zn-1 at. The test conditions for the% Ho alloy wrought material were the same.
引張試験および圧縮試験の結果を表２に併せて示した。 Table 2 shows the results of the tensile test and the compression test.
引張降伏強度３０３ＭＰａ、破断伸び２０％の高強度・高延性が確認された。また、圧縮降伏強度２９０ＭＰａが確認され、引張強度と同等の圧縮強度を示すことが確認された。高強度で高延性を有するとともに、圧縮強度の高いマグネシウム合金展伸材であることがわかる。 It was confirmed that the tensile strength was 303 MPa and the elongation at break was 20%. Moreover, the compressive yield strength of 290 MPa was confirmed, and it was confirmed that the compressive yield strength was equivalent to the tensile strength. It can be seen that this is a magnesium alloy wrought material having high strength and high ductility and high compressive strength.
また、破壊靭性値を求めた。押出し材から三点曲げ試験片を採取し、破壊靭性試験を行った。平面ひずみ破壊靭性値は、３２．５ＭＰａ・ｍ１/2と求まり、高靭性が確認された。
＜８＞Ｍｇ−２．６ａｔ％Ｚｎ−０．４ａｔ％（Ｄｙ，Ｇｄ，Ｔｂ，Ｅｒ）合金
（実験Ｎｏ．２０〜２３）
上記＜７＞Ｍｇ−Ｚｎ−Ｙの合金と同様にして、押出し比を変更、もしくは同じとしてＭｇ−Ｚｎ−Ｄｙ（実験Ｎｏ．２０）、Ｍｇ−Ｚｎ−Ｇｄ（実験Ｎｏ．２１）、Ｍｇ−Ｚｎ−Ｔｂ（実験Ｎｏ．２２）、Ｍｇ−Ｚｎ−Ｅｒ（実験Ｎｏ．２３）の各々の押出し材を得た。この各々についての組織、観察の結果と、破断伸び、降伏強度、平面ひずみ破壊靭性値の測定結果を表２に示した。Further, the fracture toughness value was obtained. A three-point bending specimen was taken from the extruded material and subjected to a fracture toughness test. The plane strain fracture toughness value was found to be 32.5 MPa · m 1/2 , confirming high toughness.
<8> Mg-2.6 at% Zn-0.4 at% (Dy, Gd, Tb, Er) alloy (Experiment No. 20 to 23)
Similar to the above <7> Mg—Zn—Y alloy, the extrusion ratio was changed or the same, Mg—Zn—Dy (Experiment No. 20), Mg—Zn—Gd (Experiment No. 21), Mg— Extruded materials of Zn-Tb (Experiment No. 22) and Mg-Zn-Er (Experiment No. 23) were obtained. Table 2 shows the structure, observation results, and measurement results of elongation at break, yield strength, and plane strain fracture toughness for each of these.
高強度、高延性、そして高靭性な特性を有するものであることが確認された。 It was confirmed to have high strength, high ductility, and high toughness.
Claims (4)
Ｍｇ１００−ａＺｎａ（ａは原子％を示し、１．６≦ａ≦８．０である）
で表わされ、マグネシウム母相中に、少なくとも亜鉛を含み、球状で、平均粒径が５００ｎｍ以下である第二相粒子が析出しているマグネシウム合金であって、当該マグネシウム母相の平均結晶粒径は１５μｍ以下であり、第二相粒子のアスペクト比が５：１以下であることを特徴とするマグネシウム合金。 The alloy composition is:
Mg 100-a Zn a (a represents atomic%, and 1.6 ≦ a ≦ 8.0)
A magnesium alloy in which second phase particles containing at least zinc and having a spherical shape and an average particle size of 500 nm or less are precipitated in the magnesium matrix, and the average crystal grains of the magnesium matrix A magnesium alloy having a diameter of 15 μm or less and an aspect ratio of second phase particles of 5: 1 or less.
Ｍｇ１００−（ａ＋ｂ）ＺｎａＣａｂ
（ａ、ｂは原子％を示し、０＜ｂ≦５．７において、０．３≦ａ≦８．５であることを示す。）
で表わされ、マグネシウム母相中に、少なくとも亜鉛を含み、球状で、平均粒径が５００ｎｍ以下である第二相粒子が析出しているマグネシウム合金であって、当該マグネシウム母相の平均結晶粒径は１５μｍ以下であり、第二相粒子のアスペクト比が５：１以下であることを特徴とするマグネシウム合金。 The alloy composition is:
Mg 100- (a + b) Zn a Ca b
(A and b represent atomic%, and in 0 <b ≦ 5.7, 0.3 ≦ a ≦ 8.5.)
A magnesium alloy in which second phase particles containing at least zinc and having a spherical shape and an average particle size of 500 nm or less are precipitated in the magnesium matrix, and the average crystal grains of the magnesium matrix A magnesium alloy having a diameter of 15 μm or less and an aspect ratio of second phase particles of 5: 1 or less.
ＫＡ＝第二相粒子の平均粒径／マグネシウム母相の平均結晶粒径 According to claim 1 or 2 ratio K A between the average crystal grain size of the second phase the average particle size of magnesium matrix of particles represented by the following formula is characterized in that from 0.005 to 0.2 Magnesium alloy.
K A = average particle size of second phase particles / average crystal particle size of magnesium matrix
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| JP6587174B2 (en) * | 2015-04-28 | 2019-10-09 | 国立研究開発法人物質・材料研究機構 | High toughness magnesium-based alloy extender and method for producing the same |
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| US10113216B2 (en) * | 2015-02-06 | 2018-10-30 | North University Of China | Quasicrystal and alumina mixed particulate reinforced magnesium-based composite material and method for manufacturing the same |
| US10844461B2 (en) | 2015-02-06 | 2020-11-24 | North University Of China | Method for manufacturing quasicrystal and alumina mixed particulate reinforced magnesium-based composite material |
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| JP2014040672A (en) | 2014-03-06 |
| JP5804431B2 (en) | 2015-11-04 |
| JPWO2008016150A1 (en) | 2009-12-24 |
| WO2008016150A1 (en) | 2008-02-07 |
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