JP2010059480A - METHOD FOR PRODUCING Ti PARTICLE-DISPERSED MAGNESIUM-BASED COMPOSITE MATERIAL - Google Patents

METHOD FOR PRODUCING Ti PARTICLE-DISPERSED MAGNESIUM-BASED COMPOSITE MATERIAL Download PDF

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JP2010059480A
JP2010059480A JP2008226260A JP2008226260A JP2010059480A JP 2010059480 A JP2010059480 A JP 2010059480A JP 2008226260 A JP2008226260 A JP 2008226260A JP 2008226260 A JP2008226260 A JP 2008226260A JP 2010059480 A JP2010059480 A JP 2010059480A
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magnesium
powder
composite material
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JP4397425B1 (en
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Katsuyoshi Kondo
勝義 近藤
Kantaro Kaneko
貫太郎 金子
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Kurimoto Ltd
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Priority to EP09811322A priority patent/EP2327808A1/en
Priority to CN200980114389XA priority patent/CN102016094A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F2009/0804Dispersion in or on liquid, other than with sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Ti particle-dispersed magnesium-based composite material having excellent strength by uniformly dispersing titanium particles into a magnesium matrix and improving boundary adhesion between titanium and magnesium. <P>SOLUTION: The Ti particle-dispersed magnesium-based composite material is obtained by uniformly dispersing titanium particles into the matrix of magnesium. Magnesium composing the matrix and the titanium particles are coupled so as to exhibit satisfactory wettability without interposing titanium oxides in their boundaries, thus the material has a tensile strength of ≥230 MPa. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、マグネシウム合金に関するものであり、特に、強度と延性の両方を向上することにより、家電製品、自動車用部品、航空機用部材など幅広い分野で使用可能なチタン(Ti)粒子分散マグネシウム基複合材料およびその製造方法に関するものである。   TECHNICAL FIELD The present invention relates to a magnesium alloy, and in particular, by improving both strength and ductility, titanium (Ti) particle-dispersed magnesium-based composite that can be used in a wide range of fields such as home appliances, automotive parts, and aircraft members. The present invention relates to a material and a manufacturing method thereof.

マグネシウム(Mg)は工業用金属材料のなかで最も比重が小さいことから、軽量化ニーズが強い二輪車、自動車、航空機などの部品や部材への利用が期待されている。しかしながら、鉄鋼材料やアルミニウム合金などの従来の工業用材料と比較すると強度が十分でないので、マグネシウム合金の利用は限定されているのが現状である。   Magnesium (Mg) has the smallest specific gravity among industrial metal materials, and is expected to be used for parts and components such as motorcycles, automobiles, and aircraft that have strong needs for weight reduction. However, since the strength is not sufficient compared with conventional industrial materials such as steel materials and aluminum alloys, the use of magnesium alloys is currently limited.

このような課題を解決すべく、マグネシウムよりも高強度で高硬度の特性を有する粒子やファイバーなどを第2相として分散する複合材料の開発が進められている。分散する有効な第2相としてチタン(Ti)が考えられる。剛性を比較すると、Mg:45GPa、Ti:105GPaであり、硬さを比較すると、Mg:35〜45Hv(ビッカース硬さ)、Ti:110〜120Hvであることから、チタン粒子をマグネシウム素地中に分散することにより、マグネシウム基複合材料の強度および硬度を向上できる効果が期待できる。   In order to solve such a problem, development of a composite material in which particles or fibers having properties higher in strength and hardness than magnesium are dispersed as the second phase is being advanced. Titanium (Ti) is considered as an effective second phase to be dispersed. When comparing the rigidity, it is Mg: 45 GPa, Ti: 105 GPa, and comparing the hardness, Mg: 35-45 Hv (Vickers hardness), Ti: 110-120 Hv, so the titanium particles are dispersed in the magnesium substrate By doing so, an effect of improving the strength and hardness of the magnesium-based composite material can be expected.

また従来の複合材料では、酸化物、炭化物、窒化物などのセラミックス系粒子やセラミックス系ファイバーの分散が主流であったが、これらの粒子やファイバーはいずれも高い剛性および硬度を有するものの、延性に乏しいために、それらがマグネシウム合金に分散した際に複合材料そのものの延性(例えば、破断伸び)を低下させる。これに対して、チタンは金属であり、それ自体が延性に優れることから、チタン粒子をマグネシウムに添加・分散した際に複合材料の延性を低下させる問題はない。   Also, in conventional composite materials, the dispersion of ceramic particles such as oxides, carbides and nitrides and ceramic fibers has been the mainstream, but these particles and fibers all have high rigidity and hardness, but are not ductile. Because they are scarce, they reduce the ductility (eg, elongation at break) of the composite material itself when dispersed in the magnesium alloy. On the other hand, since titanium is a metal and itself has excellent ductility, there is no problem of reducing the ductility of the composite material when titanium particles are added to and dispersed in magnesium.

他方、マグネシウムは耐腐食性に劣るといった問題がある。これはマグネシウムが卑なる特性を有しており、例えば、標準電極電位Es(水素HをゼロVとする)が−2.356Vと小さい。このようなマグネシウムの中に例えば、鉄(Fe:Es=−0.44V)や銅(Cu:Es=+0.34V)が少量含まれると、Mg−FeおよびMg−Cu間の電位差によってガルバニック腐食現象が進行する。これに対してチタンの標準電極電位は−1.75Vであり、Mgへの添加元素であるアルミニウム(Al:Es=−1.676V)と比較しても、Mgとの電位差はより小さい。すなわち、チタンをマグネシウムに分散することによる腐食現象への影響は小さいといえる。   On the other hand, magnesium has a problem of inferior corrosion resistance. This has the characteristic that magnesium is a base, and for example, the standard electrode potential Es (hydrogen H is set to zero V) is as small as -2.356V. For example, when a small amount of iron (Fe: Es = −0.44V) or copper (Cu: Es = + 0.34V) is contained in such magnesium, galvanic corrosion is caused by a potential difference between Mg—Fe and Mg—Cu. The phenomenon progresses. On the other hand, the standard electrode potential of titanium is −1.75 V, and the potential difference with Mg is smaller even when compared with aluminum (Al: Es = 1.676 V) which is an additive element to Mg. That is, it can be said that the influence on the corrosion phenomenon by dispersing titanium in magnesium is small.

以上のことから、マグネシウム素地中への分散強化材としてチタン粒子を用いることは、有効であると考えられる。   From the above, it is considered effective to use titanium particles as a dispersion reinforcing material in a magnesium base.

これまでに報告されているTi粒子分散マグネシウム複合材料に関する技術として、例えば、非特許文献1として、日本金属学会講演概要(2008年3月26日)p.355、No.464(片岡、北薗:Ti粒子分散Mg基複合材料の機械的特性に及ぼす微細組織の影響)、非特許文献2として、軽金属学会講演概要(2008年5月11日)p.13、No.7(北薗、片岡、駒津:マグネシウムの機械的特性に及ぼすチタン粒子添加の影響)、非特許文献3として、粉体粉末冶金講演概要集(2007年6月6日)p.148、No.2−51A(榎並、藤田、大原、五十嵐:バルクメカニカルアロイング法によるマグネシウム複合材料の開発)、非特許文献4として、粉体および粉末冶金、第55巻、第4号(2008)、p.244(榎並、藤田、本江、大原、五十嵐、近藤:バルクメカニカルアロイング法によるマグネシウム複合材料の開発)、非特許文献5として、軽金属、第54巻、第11号(2004)、p.522−526(佐藤、渡辺、三浦、三浦:遠心力固相法によるチタン粒子分散マグネシウム基傾斜機能材料の開発)などがある。   As a technique related to the Ti particle-dispersed magnesium composite material reported so far, for example, Non-Patent Document 1, Outline of the Japan Institute of Metals (March 26, 2008) p. 355, no. 464 (Kataoka, Hokuto: Influence of microstructure on mechanical properties of Ti particle-dispersed Mg-based composites), Non-Patent Document 2, Outline of Light Metal Society Presentation (May 11, 2008) p. 13, no. 7 (Hokkaido, Kataoka, Komatsu: Influence of titanium particle addition on mechanical properties of magnesium), Non-Patent Document 3, Summary of Powder Powder Metallurgy Lecture (June 6, 2007) p. 148, no. 2-51A (Inami, Fujita, Ohara, Igarashi: Development of magnesium composite material by bulk mechanical alloying method), Non-Patent Document 4, Powder and Powder Metallurgy, Vol. 55, No. 4 (2008), p. 244 (Maminami, Fujita, Motoe, Ohara, Igarashi, Kondo: Development of magnesium composite material by bulk mechanical alloying method), Non-Patent Document 5, Light Metal, Vol. 54, No. 11 (2004), p. 522-526 (Sato, Watanabe, Miura, Miura: Development of titanium particle-dispersed magnesium-based functionally gradient material by centrifugal solid phase method).

非特許文献1および非特許文献2においては、純マグネシウム板の表面に純チタン粒子を散布し、その上に純マグネシウム板を載せた状態で加熱および加圧することにより、チタン粒子を純マグネシウム板で挟みこんだ状態の複合材料を作製し、さらにこの複合材料を重ねて加熱および加圧することにより、チタン粒子が板の平面方向に配列したTi粒子分散マグネシウム基複合材料を作製することが開示されている。   In Non-Patent Document 1 and Non-Patent Document 2, pure titanium particles are dispersed on the surface of a pure magnesium plate, and heated and pressed in a state where the pure magnesium plate is placed thereon, thereby the titanium particles are made of pure magnesium plate. It is disclosed that a composite material in a sandwiched state is manufactured, and further, this composite material is stacked and heated and pressed to prepare a Ti particle-dispersed magnesium-based composite material in which titanium particles are arranged in the plane direction of the plate. Yes.

非特許文献3および非特許文献4には、マグネシウム合金粉末と純チタン粉末とを混合し、金型内に充填した状態で強塑性加工を連続的に付与した後、熱間押出加工を施すことにより、Ti粒子分散マグネシウム基複合材料を作製することが開示されている。   In Non-Patent Document 3 and Non-Patent Document 4, a magnesium alloy powder and a pure titanium powder are mixed and subjected to hot extrusion after continuously giving a strong plastic working in a state filled in a mold. To manufacture a Ti particle-dispersed magnesium-based composite material.

上記の非特許文献1〜4のいずれの場合においても、加熱温度はマグネシウムの融点を十分に下回る温度とし、溶融することなく完全な固相温度域において複合材料を作製している。それぞれの複合材料に関する引張試験の結果において、Ti粒子を添加しない材料と比較して約5〜10%の強度増加が確認されたものの、延性(破断伸び)は約20〜30%低下している。これはマグネシウムとチタンとが化合物を形成しないため、両者の接合界面強度が十分でないことから、強度向上は十分でなく、反面、界面が応力集中部となり延性低下が生じたものと認められる。   In any case of the above non-patent documents 1 to 4, the heating temperature is set to a temperature sufficiently lower than the melting point of magnesium, and the composite material is produced in a complete solid phase temperature range without melting. As a result of the tensile test for each composite material, although an increase in strength of about 5 to 10% was confirmed as compared with the material without adding Ti particles, the ductility (breaking elongation) was reduced by about 20 to 30%. . This is because magnesium and titanium do not form a compound, so that the strength of the bonding interface between the two is not sufficient, and thus the strength is not sufficiently improved. On the other hand, it is recognized that the interface becomes a stress concentration part and ductility is reduced.

以上のように、チタン粒子分散マグネシウム基複合材料において強度と延性の両者を顕著に向上させるには、Mg−Tiの界面における密着性を向上させる必要がある。   As described above, in order to significantly improve both strength and ductility in the titanium particle-dispersed magnesium-based composite material, it is necessary to improve the adhesion at the Mg—Ti interface.

非特許文献5には、固相として存在するチタン粒子を含むマグネシウムまたはマグネシウム合金(AZ91D)の溶湯中に遠心力を印加し、分散粒子と溶湯との密度差に起因する遠心力の差により生じる移動速度差を用いて組成傾斜を制御する製造方法が記載されている。チタンの比重はマグネシウムの比重の2倍以上であるので、非特許文献5に開示された遠心力固相法によって、チタン粒子をマグネシウムまたはマグネシウム合金の溶湯中に均一に分散させることは困難である。実際に、この文献には、「この手法によってチタン粒子を分散させることは困難であることがわかった。」と記載されている。さらに、この文献には、アルミニウムを含むマグネシウム合金(AZ91D)の溶湯中にチタン粒子を投入して遠心力固相法を適用した場合、チタン粒子凝集部にアルミニウム濃度が非常に多くなっていること、およびチタン粒子の外周部にアルミニウムが固溶した領域も存在していたことが記載されている。その理由として、この文献には、「高アルミニウム濃度の初期融液が毛管現象によってチタン粒子間に浸透し、その凝集・焼結に関与した可能性がある。このように、アルミニウムを含むAZ91D合金に遠心力固相法を用いることは、融液組成から考えて問題があることが判明した。」と記載されている。
日本金属学会講演概要(2008年3月26日)p.355、No.464(片岡、北薗:Ti粒子分散Mg基複合材料の機械的特性に及ぼす微細組織の影響) 軽金属学会講演概要(2008年5月11日)p.13、No.7(北薗、片岡、駒津:マグネシウムの機械的特性に及ぼすチタン粒子添加の影響) 粉体粉末冶金講演(2007年6月6日)p.148、No.2−51A(榎並、藤田、大原、五十嵐:バルクメカニカルアロイング法によるマグネシウム複合材料の開発) 粉体および粉末冶金、第55巻、第4号(2008)、p.244(榎並、藤田、本江、大原、五十嵐、近藤:バルクメカニカルアロイング法によるマグネシウム複合材料の開発) 軽金属、第54巻、第11号(2004)、p.522−526(佐藤、渡辺、三浦、三浦:遠心力固相法によるチタン粒子分散マグネシウム基傾斜機能材料の開発)
In Non-Patent Document 5, a centrifugal force is applied to a molten magnesium or magnesium alloy (AZ91D) containing titanium particles present as a solid phase, and the difference is caused by a difference in centrifugal force caused by a density difference between the dispersed particles and the molten metal. A manufacturing method is described in which the composition gradient is controlled using a difference in moving speed. Since the specific gravity of titanium is more than twice the specific gravity of magnesium, it is difficult to uniformly disperse titanium particles in a molten magnesium or magnesium alloy by the centrifugal solid phase method disclosed in Non-Patent Document 5. . Actually, this document states that “it was difficult to disperse titanium particles by this method”. Furthermore, in this document, when titanium particles are introduced into a molten magnesium alloy containing aluminum (AZ91D) and the centrifugal solid phase method is applied, the aluminum concentration in the titanium particle agglomerated portion is very high. In addition, it is described that there was a region where aluminum was dissolved in the outer peripheral portion of the titanium particles. The reason for this is that, in this document, there is a possibility that an initial melt with a high aluminum concentration permeates between titanium particles by capillary action and participates in the aggregation and sintering. Thus, an AZ91D alloy containing aluminum It has been found that the use of the centrifugal solid phase method has a problem in view of the melt composition. "
Outline of the Japan Institute of Metals (March 26, 2008) p. 355, no. 464 (Kataoka, Hokuto: Influence of microstructure on mechanical properties of Ti particle-dispersed Mg-based composites) Outline of the Japan Institute of Light Metals (May 11, 2008) p. 13, no. 7 (Hokkaido, Kataoka, Komatsu: Effect of titanium particle addition on the mechanical properties of magnesium) Powder Powder Metallurgy Lecture (June 6, 2007) p. 148, no. 2-51A (Inami, Fujita, Ohara, Igarashi: Development of magnesium composite material by bulk mechanical alloying method) Powder and Powder Metallurgy, Vol. 55, No. 4 (2008), p. 244 (Inami, Fujita, Motoe, Ohara, Igarashi, Kondo: Development of magnesium composites by bulk mechanical alloying) Light Metal, Vol. 54, No. 11 (2004), p. 522-526 (Sato, Watanabe, Miura, Miura: Development of functionally graded magnesium-based functionally dispersed titanium particles by centrifugal solid phase method)

本発明は、上記の課題を解決するためになされたものであり、その目的は、マグネシウム素地中にチタン粒子を均一に分散させるとともに、チタンとマグネシウムとの界面密着性を向上させることによって、優れた強度を持つTi粒子分散マグネシウム基複合材料を提供することである。   The present invention has been made in order to solve the above-mentioned problems, and its purpose is to achieve excellent dispersion by uniformly dispersing titanium particles in a magnesium substrate and improving interfacial adhesion between titanium and magnesium. It is to provide a Ti particle-dispersed magnesium-based composite material having high strength.

本発明に従ったTi粒子分散マグネシウム基複合材料は、マグネシウムの素地中にチタン粒子を均一に分散させたものである。その特徴は、素地を構成するマグネシウムとチタン粒子とが、それらの界面にチタン酸化物を介在させること無く良好な濡れ性を発揮して結合していること、およびマグネシウム基複合材料が230MPa以上の引張強度を有していることにある。   The Ti particle-dispersed magnesium-based composite material according to the present invention is obtained by uniformly dispersing titanium particles in a magnesium substrate. The feature is that the magnesium and titanium particles constituting the substrate are bonded with good wettability without interposing titanium oxide at the interface between them, and the magnesium-based composite material is 230 MPa or more. It has a tensile strength.

本発明によれば、適正量のチタン粒子がマグネシウムの素地中に良好な濡れ性を発揮して均一に分散しているからこそ、230MPa以上の高い引張強度を有するマグネシウム基複合材料が得られる。   According to the present invention, a magnesium-based composite material having a high tensile strength of 230 MPa or more can be obtained because an appropriate amount of titanium particles exhibits good wettability in the magnesium substrate and is uniformly dispersed.

本発明の一つの実施形態は、上記のTi粒子分散マグネシウム基複合材料を製造するための粉末に向けられるものである。この粉末は、チタン粒子がマグネシウム素地中に均一に分散している鋳造材を粉末となるように機械加工することによって得られる。   One embodiment of the present invention is directed to a powder for producing the above Ti particle-dispersed magnesium-based composite material. This powder can be obtained by machining a cast material in which titanium particles are uniformly dispersed in a magnesium base so as to become a powder.

本発明の他の実施形態における粉末は、上記のTi粒子分散マグネシウム基複合材料を製造するための粉末であって、チタン粒子が均一に分散しているマグネシウムの溶湯をアトマイズ法によって粉末状に凝固させることによって得られる。   The powder according to another embodiment of the present invention is a powder for producing the above Ti particle-dispersed magnesium-based composite material, and a molten magnesium in which titanium particles are uniformly dispersed is solidified into a powder by an atomizing method. To obtain.

本発明に従ったTi粒子分散マグネシウム基複合材料の製造方法は、マグネシウムの溶湯中にチタン粒子を投入する工程と、チタン粒子が溶湯内で均一に分散するように溶湯を撹拌する工程と、溶湯を凝固させてマグネシウムの素地中にチタン粒子を均一に分散させた複合素材を得る工程と、複合素材に対して熱間塑性加工を施して引張強度が230MPa以上のマグネシウム基複合材料を得る工程とを備える。   A method for producing a Ti particle-dispersed magnesium-based composite material according to the present invention includes a step of introducing titanium particles into a magnesium melt, a step of stirring the melt so that the titanium particles are uniformly dispersed in the melt, A step of obtaining a composite material in which titanium particles are uniformly dispersed in a magnesium substrate, and a step of subjecting the composite material to hot plastic processing to obtain a magnesium-based composite material having a tensile strength of 230 MPa or more. Is provided.

一つの実施形態では、上記の複合素材を得る工程は、溶湯を凝固させてマグネシウムの素地中にチタン粒子を分散させた鋳造材を得ることと、鋳造材に対して機械加工を施して粉末状にすることと、粉末を圧粉固化して圧粉成形体を得ることとを含む。   In one embodiment, the step of obtaining the composite material includes obtaining a cast material in which the molten metal is solidified and titanium particles are dispersed in a magnesium base, and the cast material is subjected to machining to obtain a powder form. And solidifying the powder to obtain a green compact.

他の実施形態では、上記の複合素材を得る工程は、溶湯をアトマイズ法によって粉末状に凝固させることと、粉末を圧粉固化して圧粉成形体を得ることとを含む。   In another embodiment, the step of obtaining the composite material includes solidifying the molten metal into a powder by an atomizing method, and compacting the powder to obtain a compacted body.

他の局面において、この発明に従ったTi粒子分散マグネシウム基複合材料の製造方法は、マグネシウム粉末とチタン粒子とを混合する工程と、混合粉末をマグネシウム粉末の液相発生温度よりも高い温度に保持する工程と、高い温度に保持された混合粉末を焼結固化する工程と、焼結固化体に対して熱間塑性加工を施して引張強度が230MPa以上のマグネシウム基複合材料を得る工程とを備える。   In another aspect, a method for producing a Ti particle-dispersed magnesium-based composite material according to the present invention includes a step of mixing magnesium powder and titanium particles, and the mixed powder is held at a temperature higher than the liquid phase generation temperature of the magnesium powder. A step of sintering and solidifying the mixed powder held at a high temperature, and a step of subjecting the sintered solidified body to hot plastic working to obtain a magnesium-based composite material having a tensile strength of 230 MPa or more. .

上記に記載の本発明の構成の技術的意義または作用効果については、以下の項目で詳細に説明する。   The technical significance or effects of the configuration of the present invention described above will be described in detail in the following items.

本願の発明者らは、チタンとマグネシウムとの界面密着性の向上を可能としたチタン粒子分散マグネシウム複合材料を開発すべく、両者の濡れ性に着目し、その特性評価を行なうとともに、優れた濡れ性を利用した複合材料の製造方法の検討を行った。   In order to develop a titanium particle-dispersed magnesium composite material capable of improving the interfacial adhesion between titanium and magnesium, the inventors of the present application focused on the wettability of both, evaluated the characteristics, and achieved excellent wetting. The manufacturing method of the composite material using the property was investigated.

(1)純マグネシウムと純チタンとの濡れ性
本願の発明者らは、純チタン板と純マグネシウム液滴との濡れ性を調べた。具体的には、高真空状態において溶融した純マグネシウムの液滴(800℃に保持)を酸化マグネシウム(MgO)製ノズル先端から純チタン板表面に静的に配置し、800℃における純Mgと純Tiとの濡れ性を連続撮影して評価した。その結果を図1に示す。
(1) Wettability between pure magnesium and pure titanium The inventors of the present application investigated wettability between a pure titanium plate and pure magnesium droplets. Specifically, pure magnesium droplets melted in a high vacuum state (maintained at 800 ° C.) are statically placed on the surface of the pure titanium plate from the tip of the magnesium oxide (MgO) nozzle, and pure Mg and pure at 800 ° C. The wettability with Ti was evaluated by continuous shooting. The result is shown in FIG.

図1に示すようにTi板表面に接触した時点(t=0秒)で濡れ角は約50°となり、時間の経過と共に濡れ角は減少して6分後には13°に至った。一般に濡れ角が90°を下回ると濡れ現象が生じたと判断し、その値が0°に近づくにつれて濡れ性が向上する。マグネシウムとの濡れ性が良好と言われる炭化チタニウム(TiC)は、900℃において濡れ角が約33°(参考文献:A. Contrerasaら:Scripta Materialia, 48 (2003) 1625-1630)であることを考えると、純Mgと純Tiとの濡れ性は極めて良好であると認められる。   As shown in FIG. 1, the wetting angle was about 50 ° at the time of contact with the Ti plate surface (t = 0 second), and the wetting angle decreased with time and reached 13 ° after 6 minutes. Generally, when the wetting angle is less than 90 °, it is determined that a wetting phenomenon has occurred, and the wettability improves as the value approaches 0 °. Titanium carbide (TiC), which is said to have good wettability with magnesium, has a wetting angle of about 33 ° at 900 ° C (reference: A. Contrerasa et al .: Scripta Materialia, 48 (2003) 1625-1630). Considering, it is recognized that the wettability between pure Mg and pure Ti is very good.

濡れ性の評価後に、試験片上で凝固後の純Mgとチタン板との界面を走査型電子顕微鏡(SEM)で観察した。その結果を図2に示す。溶融したMgはチタン板と接触した全域に亘り、隙間・空隙なく良好に密着していることが認められる。   After the wettability evaluation, the interface between the pure Mg and the titanium plate after solidification on the test piece was observed with a scanning electron microscope (SEM). The result is shown in FIG. It can be seen that the molten Mg is in good contact with the titanium plate without gaps or voids over the entire area.

比較のために、従来技術(非特許文献1〜4)で報告されているような複合材料、すなわちマグネシウム粉末の固相温度で純チタン粉末と純マグネシウム粉末の混合粉末を加熱および加圧した複合材料を作製し、両者の接合界面を観察した。その結果を図3に示す。複合材料を作製するにあたり、加熱温度を520度とし、純マグネシウムの融点(650度)よりも低く設定して完全固相状態とした。矢印で示すようにTi粒子とMg素地との界面には、多数の隙間・空隙が観察されており、密着性が十分でないことがわかる。したがって、従来技術で開示されている製造方法においては、Mgの融点を下回る固相温度で加熱・焼結するためMgとTiとの密着性が十分でなく、その結果、複合材料における強度および延性の向上が得られなかったと考えられる。   For comparison, a composite material as reported in the prior art (Non-Patent Documents 1 to 4), that is, a composite in which a mixed powder of pure titanium powder and pure magnesium powder is heated and pressed at a solid phase temperature of magnesium powder. Materials were prepared and the bonding interface between the two was observed. The result is shown in FIG. In producing the composite material, the heating temperature was set to 520 ° C., and the temperature was set lower than the melting point of pure magnesium (650 ° C.) to obtain a completely solid state. As indicated by the arrows, a large number of gaps / voids are observed at the interface between the Ti particles and the Mg substrate, indicating that the adhesion is not sufficient. Therefore, in the manufacturing method disclosed in the prior art, the adhesion between Mg and Ti is not sufficient because it is heated and sintered at a solid phase temperature lower than the melting point of Mg. As a result, the strength and ductility of the composite material It is considered that the improvement was not obtained.

(2)Ti粒子分散マグネシウム溶湯を用いた複合材料
本発明者らは、上記の結果に基づき、マグネシウム素地とTi粒子との界面の密着性を向上させるために、以下の方法でTi粒子分散マグネシウム基複合材料を作製した。まず、素地を構成するマグネシウムあるいはマグネシウム合金の融点よりも高い温度にマグネシウム溶湯を保持し、この溶湯中に適正量のTi粒子を添加した。チタン粒子が溶湯中で均一に分散するように溶湯を十分に撹拌した後に、溶湯を凝固させた。このような製法で作製したマグネシウム基複合素材においては、素地を構成するマグネシウムとチタン粒子とが、それらの界面にチタン酸化物を介在させること無く、良好な濡れ性を発揮して優れた密着性を持って結合している。このマグネシウム基複合素材に対して熱間塑性加工を施すことによって、230MPa以上の引張強度を有するTi粒子分散マグネシウム基複合材料を得ることができた。
(2) Composite Material Using Molten Ti Particle Dispersed Magnesium Based on the above results, the present inventors have developed the following method to improve the adhesion of the interface between the magnesium base and Ti particles. A matrix composite material was prepared. First, the molten magnesium was held at a temperature higher than the melting point of magnesium or magnesium alloy constituting the substrate, and an appropriate amount of Ti particles was added to the molten metal. The molten metal was sufficiently stirred so that the titanium particles were uniformly dispersed in the molten metal, and then the molten metal was solidified. In the magnesium-based composite material produced by such a manufacturing method, magnesium and titanium particles constituting the substrate exhibit excellent wettability without interposing titanium oxide at the interface between them, and excellent adhesion Have joined. By subjecting this magnesium-based composite material to hot plastic working, a Ti particle-dispersed magnesium-based composite material having a tensile strength of 230 MPa or more could be obtained.

チタン粒子をマグネシウム素地中に均一に分散させた複合素材は、従来の鋳造法やダイキャスト法などによっても製造することが可能である。またそれらの鋳造材に対して切削加工や粉砕加工などの機械加工を施して粉末状にすることができる。このようにして得られたマグネシウム基複合粉末においては、チタン粒子がマグネシウムの素地中に均一に分散している。このマグネシウム基複合粉末の組織写真の一例を図4に示す。図4を参照すれば明らかなように、Ti粒子とMg素地との界面には空隙は見られず、良好な密着性を有していることが認められる。   A composite material in which titanium particles are uniformly dispersed in a magnesium substrate can be produced by a conventional casting method, die casting method, or the like. Further, these cast materials can be made into powder by machining such as cutting and grinding. In the magnesium-based composite powder thus obtained, the titanium particles are uniformly dispersed in the magnesium base. An example of the structure photograph of this magnesium-based composite powder is shown in FIG. As is apparent from FIG. 4, no voids are observed at the interface between the Ti particles and the Mg substrate, and it is recognized that the film has good adhesion.

チタン粒子をマグネシウム素地中に均一に分散させたマグネシウム基複合粉末は、チタン粒子を均一に分散させているマグネシウムの溶湯をアトマイズ法によって凝固させることによっても得られる。具体的な手法として、本発明者らは、カーボン製坩堝内で純マグネシウムを溶解し、その溶湯中に純チタン粉末(平均粒子径:29.8μm)を3mass%添加し、十分に攪拌した後、その溶湯を坩堝底部から溶湯流として排出し、この溶湯流に高圧水を噴射すること(水アトマイズ法)により、凝固した粉末を得た。得られた粉末の外観写真と粉末内部の組織観察結果を図5に示す。この水アトマイズ粉末においても、Ti粒子とMg素地との界面には空隙は見られず、良好な密着性を有していることが認められる。   A magnesium-based composite powder in which titanium particles are uniformly dispersed in a magnesium substrate can also be obtained by solidifying a molten magnesium in which titanium particles are uniformly dispersed by an atomizing method. As a specific method, the present inventors dissolved pure magnesium in a carbon crucible, added 3 mass% of pure titanium powder (average particle size: 29.8 μm) into the molten metal, and after sufficiently stirring The molten metal was discharged as a molten metal stream from the bottom of the crucible, and high pressure water was injected into the molten metal stream (water atomization method) to obtain a solidified powder. FIG. 5 shows an appearance photograph of the obtained powder and a structure observation result inside the powder. Also in this water atomized powder, it is recognized that there is no void at the interface between the Ti particles and the Mg substrate, and that the powder has good adhesion.

以上のように、マグネシウム溶湯中にチタン粒子を添加し、十分に均一攪拌処理を施した後、鋳造法あるいはダイカスト法によりマグネシウム基複合素材とする場合、あるいはチタン粒子を均一に分散させているマグネシウム溶湯をアトマイズ法によって直接粉末化する場合のいずれにおいても、チタン粒子と素地のマグネシウムとは、優れた濡れ性によって空隙のない良好な密着性を有して結合する。   As described above, after adding titanium particles into the molten magnesium and sufficiently stirring the mixture, a magnesium-based composite material is obtained by casting or die casting, or magnesium in which titanium particles are uniformly dispersed In any case where the molten metal is directly pulverized by the atomization method, the titanium particles and the base magnesium are bonded with excellent wettability and good adhesion without voids.

鋳造法またはダイキャスト法で作製したTi粒子分散マグネシウム基複合素材を所定の温度に加熱した後に、この素材に対して熱間押出加工、熱間圧延加工、鍛造加工などの熱間塑性加工を施すことで、素地の結晶粒は微細化して複合材料の強度は更に向上する。例えば、複合材料の引張強度は230MPa以上となる。   After heating the Ti particle-dispersed magnesium-based composite material produced by casting or die casting to a predetermined temperature, the material is subjected to hot plastic processing such as hot extrusion, hot rolling, and forging. As a result, the crystal grains of the substrate are refined and the strength of the composite material is further improved. For example, the tensile strength of the composite material is 230 MPa or more.

また鋳造材から切削加工等の機械加工によって作製したTi粒子分散マグネシウム基複合粉末、または溶湯流に高圧水や高圧ガスを噴射して得られたTi粒子分散マグネシウム基複合粉末を圧粉固化して圧粉成形体や焼結固化体を作製し、必要に応じて引き続いて熱間押出加工、熱間圧延加工、鍛造加工などの熱間塑性加工を施すことにより、複合粉末同士を冶金的に結合または焼結したTi粒子分散マグネシウム基複合材料を創製することが可能である。   In addition, Ti particle-dispersed magnesium-based composite powder produced by machining such as cutting from a cast material, or Ti particle-dispersed magnesium-based composite powder obtained by injecting high-pressure water or high-pressure gas into a molten metal stream is compacted and solidified. Composite powders are metallurgically bonded by producing green compacts and sintered solidified bodies, followed by hot plastic processing such as hot extrusion, hot rolling and forging, as necessary. Alternatively, it is possible to create a sintered Ti particle-dispersed magnesium-based composite material.

上記の実施形態では、マグネシウムの溶湯中に適正量のチタン粒子を投入するものであったが、他の実施形態として、次の製法によってTi粒子分散マグネシウム基複合材料を得ることも可能である。この実施形態では、マグネシウム粉末とチタン粒子とを混合し、この混合粉末を所定の温度に保持して焼結固化する。ここで重要なことは、混合粉末をマグネシウム粉末の液相発生温度よりも高い温度に保持することである。このような高い温度に保持することにより、焼結後の焼結固化体中では、素地を構成するマグネシウムとチタン粒子とが、それらの界面にチタン酸化物を介在させること無く、良好な濡れ性を発揮して優れた密着性を持って結合したものとなる。この焼結固化体に対して熱間塑性加工を施すことによって、230MPa以上の引張強度を有するTi粒子分散マグネシウム基複合材料を得ることができる。   In the above embodiment, an appropriate amount of titanium particles is introduced into the molten magnesium. However, as another embodiment, a Ti particle-dispersed magnesium-based composite material can be obtained by the following manufacturing method. In this embodiment, magnesium powder and titanium particles are mixed, and the mixed powder is held at a predetermined temperature and sintered and solidified. What is important here is to maintain the mixed powder at a temperature higher than the liquid phase generation temperature of the magnesium powder. By maintaining such a high temperature, in the sintered solidified body after sintering, the magnesium and titanium particles constituting the substrate have good wettability without interposing titanium oxide at the interface between them. It will be bonded with excellent adhesiveness. By subjecting this sintered solidified body to hot plastic working, a Ti particle-dispersed magnesium-based composite material having a tensile strength of 230 MPa or more can be obtained.

純度99.8%の純マグネシウム塊と平均粒子径29.8μmのチタン粉末とを出発原料として準備した。純マグネシウム塊をカーボン坩堝内で750℃に加熱して溶解し、その溶湯中に上記のTi粒子を全体の重量比率で0.5mass%、1.5mass%、2.8mass%の3条件で添加した。その後、Ti粒子の偏析および底部への沈降を防ぐために、溶湯を十分に均一攪拌処理した後、水アトマイズ法によってTi粒子分散マグネシウム基複合粉末を作製した。   A pure magnesium lump having a purity of 99.8% and a titanium powder having an average particle diameter of 29.8 μm were prepared as starting materials. Pure magnesium lump is melted by heating to 750 ° C in a carbon crucible, and the above Ti particles are added to the molten metal under three conditions of 0.5 mass%, 1.5 mass%, and 2.8 mass% as a whole. did. Thereafter, in order to prevent segregation of Ti particles and sedimentation to the bottom, the molten metal was sufficiently uniformly stirred, and then a Ti particle-dispersed magnesium-based composite powder was produced by a water atomization method.

一方、比較として純度99.9%の純マグネシウム粉末(平均粒子径162μm)を準備し、上記のTi粉末の比率が0.5mass%、1.5mass%、2.8mass%となるように両者を秤量した後、乾式ボールミルを用いて混合処理を施して、Mg−Ti混合粉末を作製した。   On the other hand, pure magnesium powder (average particle size 162 μm) having a purity of 99.9% was prepared as a comparison, and both were adjusted so that the ratio of the Ti powder was 0.5 mass%, 1.5 mass%, and 2.8 mass%. After weighing, it was mixed using a dry ball mill to prepare a Mg—Ti mixed powder.

これらの粉末をカーボン型に充填し、放電プラズマ焼結装置を用いて真空雰囲気中で550℃にて30分間(加圧力:30MPa)加圧することで、粉末同士を焼結固化して直径45mmの押出用ビレットを作製した。それぞれのTi粒子分散マグネシウム粉末ビレットをアルゴンガス雰囲気中で200℃にて5分間保持し,直ちに熱間押出加工(押出比:37)を施して直径7mmの丸棒押出材を作製した。   These powders are filled in a carbon mold and pressed at 550 ° C. for 30 minutes (pressing force: 30 MPa) in a vacuum atmosphere using a discharge plasma sintering apparatus, so that the powders are sintered and solidified to have a diameter of 45 mm. An extrusion billet was prepared. Each Ti particle-dispersed magnesium powder billet was held at 200 ° C. for 5 minutes in an argon gas atmosphere and immediately subjected to hot extrusion (extrusion ratio: 37) to produce a round bar extruded material having a diameter of 7 mm.

なお、比較として、Ti粒子を含まない純マグネシウム粉末についても上記の製造手順に基づいて丸棒押出材を作製した。   For comparison, a round bar extruded material was also produced for pure magnesium powder containing no Ti particles based on the above production procedure.

得られた3種類のマグネシウム粉末押出材から引張試験片を採取し、常温にて引張強度試験を行った。Ti粒子を含まない純Mg粉末、および2つの製法により作製した2.8mass%のTi粒子を含むMg粉末をそれぞれ用いた押出材における応力−歪曲線を図6に示す。   Tensile test pieces were collected from the obtained three kinds of magnesium powder extrudates and subjected to a tensile strength test at room temperature. FIG. 6 shows stress-strain curves in extruded materials using pure Mg powder containing no Ti particles and Mg powder containing 2.8 mass% Ti particles produced by two production methods.

Ti粒子を含まない純マグネシウム粉末押出材の強度および伸び特性と比較して、本発明による水アトマイズ法を用いたTi粒子分散マグネシウム基複合粉末押出材の引張強さおよび耐力は約35〜40%増加し、また破断伸びは同等であり15%以上の高い値を示した。   Compared with the strength and elongation characteristics of pure magnesium powder extrudate containing no Ti particles, the tensile strength and yield strength of the Ti particle-dispersed magnesium-based composite powder extrudate using the water atomization method according to the present invention is about 35-40%. In addition, the elongation at break was equivalent and showed a high value of 15% or more.

一方、比較材であるTi粒子とMg粉末との混合粉末を用いて作製した押出材では、引張強さおよび耐力は僅かに3〜6%程度増加するものの、破断伸びは10%未満と低減した。引張試験後の試料破断面を観察したところ、比較材ではTi粒子とマグネシウム素地との界面において亀裂が進展しており、両者の密着性が十分でないためにTi粒子添加による強度改善効果が得られなかったことが認められた。   On the other hand, in the extruded material produced using the mixed powder of Ti particles and Mg powder as a comparative material, the tensile strength and the proof stress slightly increased by about 3 to 6%, but the elongation at break decreased to less than 10%. . When the fracture surface of the sample after the tensile test was observed, cracks progressed at the interface between the Ti particles and the magnesium substrate in the comparative material, and because the adhesion between the two was not sufficient, the effect of improving the strength by adding Ti particles was obtained. It was admitted that there was not.

Ti添加量に対する各押出材の引張強さ(TS)および耐力(YS)の変化を図7に示す。本発明による水アトマイズ法を用いたTi粒子分散マグネシウム基複合粉末押出材においては、引張強さおよび耐力は共に、Ti粒子含有量の増加に対して増大しており、Ti粒子の均一分散による高強度化の効果が確認された。これは前述したように溶湯におけるTi粒子とマグネシウムとの優れた濡れ性による両者の密着性向上による結果である。   FIG. 7 shows changes in tensile strength (TS) and proof stress (YS) of each extruded material with respect to Ti addition amount. In the Ti particle-dispersed magnesium-based composite powder extruded material using the water atomization method according to the present invention, both the tensile strength and the proof stress are increased with an increase in the Ti particle content. The effect of strengthening was confirmed. As described above, this is a result of improved adhesion between the Ti particles and magnesium in the molten metal due to excellent wettability.

一方、従来の製法であるTi粉末とMg粉末との混合粉末を用いて固相温度域で焼結・押出固化した場合、Ti粒子の添加量が増加するに連れて押出材の引張強さおよび耐力は低下する傾向にあり、Ti粒子による分散強化が十分でないことが認められた。   On the other hand, when sintered and extruded and solidified in the solid phase temperature range using a conventional mixed powder of Ti powder and Mg powder, the tensile strength of the extruded material and It was recognized that the yield strength tended to decrease and the dispersion strengthening by the Ti particles was not sufficient.

実施例1と同様に、純度99.8%の純マグネシウム塊と平均粒子径29.8μmのチタン粉末とを出発原料として準備した。マグネシウム塊をカーボン坩堝内で750℃に加熱して溶解し、その溶湯中に上記のTi粒子を全体の重量比率で1mass、3mass%、5mass%の3条件で添加した。その後、Ti粒子の偏析および底部への沈降を防ぐために、溶湯を十分に均一攪拌処理した後、円筒状金型に鋳込んで直径60mmのビレットを作製した。各鋳込みビレットから機械加工により直径45mmの押出用ビレットを作製し、各ビレットをアルゴンガス雰囲気中で200℃にて5分間保持し、直ちに熱間押出加工(押出比:37)を施して直径7mmの丸棒押出材を作製した。   As in Example 1, a pure magnesium lump having a purity of 99.8% and a titanium powder having an average particle size of 29.8 μm were prepared as starting materials. The magnesium lump was melted by heating to 750 ° C. in a carbon crucible, and the above Ti particles were added to the molten metal under three conditions of 1 mass, 3 mass%, and 5 mass% in the whole weight ratio. Thereafter, in order to prevent segregation of Ti particles and settling to the bottom, the molten metal was sufficiently uniformly stirred, and then cast into a cylindrical mold to produce a billet having a diameter of 60 mm. A billet for extrusion having a diameter of 45 mm was prepared from each cast billet by machining, each billet was held at 200 ° C. for 5 minutes in an argon gas atmosphere, and immediately subjected to hot extrusion (extrusion ratio: 37) to have a diameter of 7 mm. A round bar extruded material was prepared.

各押出材の光学顕微鏡観察結果を図8に示す。Ti粒子添加量が増加するにつれて押出材におけるTi粒子の割合も増大しており、またTi粒子を5mass%添加した場合においてもTi粒子の凝集・偏析現象は見られず、マグネシウム素地中に均一に分散していることがわかる。   The optical microscope observation result of each extruded material is shown in FIG. As the Ti particle addition amount increases, the proportion of Ti particles in the extruded material also increases, and even when 5 mass% of Ti particles are added, there is no aggregation or segregation phenomenon of Ti particles, and it is uniformly in the magnesium substrate. It can be seen that they are dispersed.

各押出材の引張試験結果を表1に示す。   Table 1 shows the tensile test results of each extruded material.

実施例1と同様に、本発明による鋳造法を用いて作製したTi粒子マグネシウム基複合材料に対して押出加工を施して得られる押出材において、Ti粒子の含有量が増加するに伴い、引張強さおよび耐力は共に増大し、しかも破断伸びの顕著な低下は見られない。以上の結果より本発明によるTi粒子分散マグネシウム基複合材料においては、Ti粒子の凝集・偏析を伴うことなく、Ti粒子の添加によってマグネシウム素材の強度向上が可能となる。   As in Example 1, in the extruded material obtained by subjecting the Ti particle magnesium-based composite material produced using the casting method according to the present invention to extrusion, as the Ti particle content increases, the tensile strength increases. Both the thickness and the proof stress increase, and there is no significant decrease in the elongation at break. From the above results, in the Ti particle-dispersed magnesium-based composite material according to the present invention, the strength of the magnesium material can be improved by the addition of Ti particles without accompanying aggregation and segregation of Ti particles.

実施例1と同様に、純度99.8%の純マグネシウム塊と平均粒子径29.8μmのチタン粉末とを出発原料として準備した。マグネシウム塊をカーボン坩堝内で750℃に加熱して溶解し、その溶湯中に上記のTi粒子を全体の重量比率で2mass%および4mass%の条件でそれぞれ添加した。その後、Ti粒子の偏析および底部への沈降を防ぐために、溶湯を十分に均一攪拌処理した後、円筒状金型に鋳込んで直径60mmのビレットを作製した。各鋳込みビレットから切削加工により全長1〜4mm程度の切粉を作製した。   As in Example 1, a pure magnesium lump having a purity of 99.8% and a titanium powder having an average particle size of 29.8 μm were prepared as starting materials. The magnesium lump was melted by heating to 750 ° C. in a carbon crucible, and the Ti particles were added to the molten metal under the conditions of 2 mass% and 4 mass%, respectively, in the total weight ratio. Thereafter, in order to prevent segregation of Ti particles and settling to the bottom, the molten metal was sufficiently uniformly stirred, and then cast into a cylindrical mold to produce a billet having a diameter of 60 mm. Chips having a total length of 1 to 4 mm were produced from each cast billet by cutting.

各切粉を組織観察した結果、Ti粒子は凝集・偏析することなくMg素地中に均一に分散していた。そして、切粉をSKD11製金型に充填して油圧プレスにより加圧力600MPaを付与して直径45mmの粉末成形体ビレットを作製した。各ビレットをアルゴンガス雰囲気中で300℃にて5分間保持し、直ちに熱間押出加工(押出比:37)を施して直径7mmの丸棒押出材を作製した。   As a result of observing the structure of each chip, the Ti particles were uniformly dispersed in the Mg substrate without being aggregated or segregated. Then, the chips were filled in a SKD11 mold and a pressure of 600 MPa was applied by a hydraulic press to produce a powder compact billet having a diameter of 45 mm. Each billet was held at 300 ° C. for 5 minutes in an argon gas atmosphere, and immediately subjected to hot extrusion (extrusion ratio: 37) to produce a round bar extruded material having a diameter of 7 mm.

それぞれのマグネシウム粉末押出材から引張試験片を採取し、常温にて引張強度試験を行ったところ、2mass%Tiを含む切粉を用いた押出材では、引張強さ:264MPa、破断伸び:15.4%、4mass%Tiを含む切粉を用いた押出材では、引張強さ:294MPa、破断伸び:13.74%が得られた。Ti粒子の添加量の増加に伴い、破断伸びの著しい低下を伴うことなく、引張強さは増大しており、また実施例1で記載した比較材の特性を比較すると、同一量のTi粒子を含む場合であっても明らかに引張強さおよび耐力は増大している。   Tensile test specimens were collected from each of the magnesium powder extrudates and subjected to a tensile strength test at room temperature. With the extrudates using chips containing 2 mass% Ti, tensile strength: 264 MPa, elongation at break: 15. In the extruded material using the chips containing 4% and 4 mass% Ti, tensile strength: 294 MPa and elongation at break: 13.74% were obtained. As the addition amount of the Ti particles is increased, the tensile strength is increased without significantly decreasing the elongation at break, and when the properties of the comparative materials described in Example 1 are compared, the same amount of Ti particles is obtained. Even when it is included, the tensile strength and the proof stress are clearly increased.

以上の結果より、上述した本発明の製法によって得られたTi粒子分散マグネシウム基複合材料では、Ti粒子の凝集・偏析を伴うことなく、Ti粒子の添加によってマグネシウム素材の強度向上が可能となる。   From the above results, in the Ti particle-dispersed magnesium-based composite material obtained by the above-described production method of the present invention, the strength of the magnesium material can be improved by the addition of Ti particles without accompanying aggregation and segregation of Ti particles.

実施例1と同様に、純度99.8%の純マグネシウム塊と平均粒子径22.8μmのチタン合金粉末(Ti−6.1Al%−3.8V/mass%)とを出発原料として準備した。マグネシウム塊をカーボン坩堝内で750℃に加熱して溶解し、その溶湯中に上記のTi合金粒子を全体の重量比率で1mass%、3mass%、5mass%の3条件で添加した。その後、Ti合金粒子の偏析および底部への沈降を防ぐために、溶湯を十分に均一攪拌処理を施した後、円筒状金型に鋳込んで直径60mmのビレットを作製した。   As in Example 1, a pure magnesium lump having a purity of 99.8% and a titanium alloy powder (Ti-6.1Al% -3.8V / mass%) having an average particle diameter of 22.8 μm were prepared as starting materials. The magnesium lump was heated and melted at 750 ° C. in a carbon crucible, and the Ti alloy particles were added to the molten metal under three conditions of 1 mass%, 3 mass%, and 5 mass% in the total weight ratio. Thereafter, in order to prevent segregation of Ti alloy particles and sedimentation to the bottom, the molten metal was sufficiently subjected to uniform stirring treatment, and then cast into a cylindrical mold to produce a billet having a diameter of 60 mm.

各鋳込みビレットから機械加工により直径45mmの押出用ビレットを作製し、各ビレットをアルゴンガス雰囲気中で200℃にて5分間保持し、直ちに熱間押出加工(押出比:37)を施して直径7mmの丸棒押出材を作製した。そして各マグネシウム粉末押出材から引張試験片を採取し、常温にて引張試験を行った。   A billet for extrusion having a diameter of 45 mm was prepared from each cast billet by machining, each billet was held at 200 ° C. for 5 minutes in an argon gas atmosphere, and immediately subjected to hot extrusion (extrusion ratio: 37) to have a diameter of 7 mm. A round bar extruded material was prepared. And the tension test piece was extract | collected from each magnesium powder extruded material, and the tension test was done at normal temperature.

その結果を表2に示す。なお、実施例2に記載の純Ti粒子を用いた際の押出材の引張強さを比較値として用いた。   The results are shown in Table 2. In addition, the tensile strength of the extrusion material at the time of using the pure Ti particle | grains described in Example 2 was used as a comparative value.

Ti−6Al−4V合金粉末を用いた場合においても、本発明によるTi粒子分散マグネシウム基複合材料においては、Ti合金粒子は凝集・偏析することなく素地中に均一に分散し、その添加量が増加するに伴い、引張強さは増大しており、また純Ti粒子を添加した場合と比較して引張強さの増加量は増大している。つまり、分散する粒子の硬度・強度がより増加することでマグネシウム複合材料の強度も更に向上する。   Even when Ti-6Al-4V alloy powder is used, in the Ti particle-dispersed magnesium-based composite material according to the present invention, Ti alloy particles are uniformly dispersed in the substrate without agglomeration and segregation, and the amount added is increased. Accordingly, the tensile strength is increased, and the amount of increase in tensile strength is increased as compared with the case where pure Ti particles are added. That is, the strength of the magnesium composite material is further improved by further increasing the hardness and strength of the dispersed particles.

以上、図面を参照してこの発明の実施形態を説明したが、この発明は、図示した実施形態のものに限定されない。図示した実施形態に対して、この発明と同一の範囲内において、あるいは均等の範囲内において、種々の修正や変形を加えることが可能である。   As mentioned above, although embodiment of this invention was described with reference to drawings, this invention is not limited to the thing of embodiment shown in figure. Various modifications and variations can be made to the illustrated embodiment within the same range or equivalent range as the present invention.

この発明は、優れた強度を有するTi粒子分散マグネシウム基複合材料およびその製造方法として、有利に利用され得る。   The present invention can be advantageously used as a Ti particle-dispersed magnesium-based composite material having excellent strength and a method for producing the same.

純マグネシウムと純チタンとの濡れ性を評価するための図および写真である。It is the figure and photograph for evaluating the wettability of pure magnesium and pure titanium. 純マグネシウムと純チタンとの界面を走査型電子顕微鏡で観察した写真である。It is the photograph which observed the interface of pure magnesium and pure titanium with the scanning electron microscope. 純チタン粉末と純マグネシウム粉末との混合粉末を加熱および加圧した後に得られた複合材料における両者の界面を走査型電子顕微鏡で観察した写真である。It is the photograph which observed the interface of both in the composite material obtained after heating and pressurizing the mixed powder of pure titanium powder and pure magnesium powder with the scanning electron microscope. チタン粒子が内部に分散したマグネシウム基複合粉末の組織写真の一例である。It is an example of the structure | tissue photograph of the magnesium group composite powder in which the titanium particle was disperse | distributed inside. 水アトマイズ法によって得られたTi粒子分散マグネシウム基複合粉末の外観写真および組織観察写真である。It is the external appearance photograph and structure | tissue observation photograph of Ti particle dispersion | distribution magnesium group composite powder obtained by the water atomization method. チタン粒子を含まない純マグネシウム粉末、および2つの製法により作製したTi粒子分散マグネシウム基複合粉末を用いた押出材の応力−歪曲線を示す図である。It is a figure which shows the stress-strain curve of the extrusion material using the pure magnesium powder which does not contain a titanium particle, and the Ti particle dispersion | distribution magnesium group composite powder produced by two manufacturing methods. チタン添加量に対する各押出材の引張強さ(TS)および耐力(YS)の変化を示す図である。It is a figure which shows the change of the tensile strength (TS) and proof stress (YS) of each extrusion material with respect to titanium addition amount. チタン粒子の含有量を変えた各押出材の光学顕微鏡観察写真である。It is the optical microscope observation photograph of each extrusion material which changed content of the titanium particle.

Claims (7)

マグネシウムの素地中にチタン粒子を均一に分散させたTi粒子分散マグネシウム基複合材料において、
素地を構成するマグネシウムとチタン粒子とが、それらの界面にチタン酸化物を介在させること無く良好な濡れ性を発揮して結合しており、230MPa以上の引張強度を有していることを特徴とする、Ti粒子分散マグネシウム基複合材料。
In a Ti particle-dispersed magnesium-based composite material in which titanium particles are uniformly dispersed in a magnesium substrate,
The magnesium and titanium particles constituting the substrate are bonded with good wettability without interposing titanium oxide at the interface between them, and have a tensile strength of 230 MPa or more. Ti-particle-dispersed magnesium-based composite material.
請求項1に記載のTi粒子分散マグネシウム基複合材料を製造するための粉末であって、
チタン粒子がマグネシウム素地中に均一に分散している鋳造材を粉末となるように機械加工することによって得られる、Ti粒子分散マグネシウム基複合粉末。
A powder for producing the Ti particle-dispersed magnesium-based composite material according to claim 1,
A Ti particle-dispersed magnesium-based composite powder obtained by machining a cast material in which titanium particles are uniformly dispersed in a magnesium base so as to become powder.
請求項1に記載のTi粒子分散マグネシウム基複合材料を製造するための粉末であって、
チタン粒子が均一に分散しているマグネシウムの溶湯をアトマイズ法によって粉末状に凝固させることによって得られる、Ti粒子分散マグネシウム基複合粉末。
A powder for producing the Ti particle-dispersed magnesium-based composite material according to claim 1,
A Ti particle-dispersed magnesium-based composite powder obtained by solidifying magnesium melt in which titanium particles are uniformly dispersed into a powder form by an atomizing method.
マグネシウムの溶湯中にチタン粒子を投入する工程と、
前記チタン粒子が前記溶湯内で均一に分散するように前記溶湯を撹拌する工程と、
前記溶湯を凝固させてマグネシウムの素地中に前記チタン粒子を均一に分散させた複合素材を得る工程と、
前記複合素材に対して熱間塑性加工を施して引張強度が230MPa以上のマグネシウム基複合材料を得る工程とを備える、Ti粒子分散マグネシウム基複合材料の製造方法。
Introducing titanium particles into the molten magnesium;
Stirring the molten metal so that the titanium particles are uniformly dispersed in the molten metal;
A step of solidifying the molten metal to obtain a composite material in which the titanium particles are uniformly dispersed in a magnesium base;
And a step of subjecting the composite material to hot plastic working to obtain a magnesium-based composite material having a tensile strength of 230 MPa or more.
前記複合素材を得る工程は、前記溶湯を凝固させてマグネシウムの素地中にチタン粒子を分散させた鋳造材を得ることと、
前記鋳造材に対して機械加工を施して粉末状にすることと、
前記粉末を圧粉固化して圧粉成形体を得ることとを含む、請求項4に記載のTi粒子分散マグネシウム基複合材料の製造方法。
The step of obtaining the composite material includes obtaining a casting material in which the molten metal is solidified and titanium particles are dispersed in a magnesium base;
Machining the cast material into a powder;
The method for producing a Ti particle-dispersed magnesium-based composite material according to claim 4, comprising solidifying the powder to obtain a green compact.
前記複合素材を得る工程は、前記溶湯をアトマイズ法によって粉末状に凝固させることと、
前記粉末を圧粉固化して圧粉成形体を得ることとを含む、請求項4に記載のTi粒子分散マグネシウム基複合材料の製造方法。
The step of obtaining the composite material includes solidifying the molten metal into a powder by an atomization method;
The method for producing a Ti particle-dispersed magnesium-based composite material according to claim 4, comprising solidifying the powder to obtain a green compact.
マグネシウム粉末とチタン粒子とを混合する工程と、
前記混合粉末をマグネシウム粉末の液相発生温度よりも高い温度に保持する工程と、
前記高い温度に保持された混合粉末を焼結固化する工程と、
前記焼結固化体に対して熱間塑性加工を施して引張強度が230MPa以上のマグネシウム基複合材料を得る工程とを備える、Ti粒子分散マグネシウム基複合材料の製造方法。
Mixing magnesium powder and titanium particles;
Maintaining the mixed powder at a temperature higher than the liquid phase generation temperature of the magnesium powder;
Sintering and solidifying the mixed powder held at the high temperature;
And a step of subjecting the sintered solidified body to hot plastic working to obtain a magnesium-based composite material having a tensile strength of 230 MPa or more.
JP2008226260A 2008-09-03 2008-09-03 Method for producing Ti particle-dispersed magnesium-based composite material Expired - Fee Related JP4397425B1 (en)

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KR1020107015461A KR20100092055A (en) 2008-09-03 2009-03-16 Magnesium-based composite material having ti particles dispersed therein, and method for production thereof
PCT/JP2009/055026 WO2010026793A1 (en) 2008-09-03 2009-03-16 Magnesium-based composite material having ti particles dispersed therein, and method for production thereof
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US13/060,078 US20110150694A1 (en) 2008-09-03 2009-03-16 METHOD FOR MANUFACTURING Ti PARTICLE-DISPERSED MAGNESIUM-BASED COMPOSITE MATERIAL

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