JP2013249512A - Molybdenum heat-resistant alloy, friction stir welding tool, and manufacturing method - Google Patents

Molybdenum heat-resistant alloy, friction stir welding tool, and manufacturing method Download PDF

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JP2013249512A
JP2013249512A JP2012124718A JP2012124718A JP2013249512A JP 2013249512 A JP2013249512 A JP 2013249512A JP 2012124718 A JP2012124718 A JP 2012124718A JP 2012124718 A JP2012124718 A JP 2012124718A JP 2013249512 A JP2013249512 A JP 2013249512A
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resistant alloy
phase
carbonitride
molybdenum heat
friction stir
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JP6202787B2 (en
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Shigekazu Yamazaki
繁一 山▲崎▼
Ayuri Tsuji
あゆ里 辻
Shigehiko Takaoka
重彦 高岡
Takanori Sumikura
孝典 角倉
Naritsune Nishino
成恒 西野
Akihiko Ikegaya
明彦 池ヶ谷
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Allied Material Corp
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    • 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
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • B22F3/14Both compacting and sintering simultaneously
    • B22F3/15Hot isostatic pressing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/12Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding
    • B23K20/122Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding using a non-consumable tool, e.g. friction stir welding
    • B23K20/1245Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding using a non-consumable tool, e.g. friction stir welding characterised by the apparatus
    • B23K20/1255Tools therefor, e.g. characterised by the shape of the probe
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04Alloys based on tungsten or molybdenum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Powder Metallurgy (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant alloy for a plastic working tool, which meets the properties, such as a bearing force and hardness, corresponding to an object to be processed which has a higher melting point than that in the past.SOLUTION: A molybdenum heat-resistant alloy includes a first phase mainly comprising Mo, a second phase mainly comprising at least one carbonitride of Ti, Zr and Hf, a third phase which is provided between the first phase and second phase and has a solid solution of Mo and at least one carbonitride of Ti, Zr and Hf, and the remainder including inevitable impurities.

Description

本発明は、高温環境下で用いられる塑性加工用工具、特に摩擦攪拌接合用工具に適したモリブデン耐熱合金とそれを用いた摩擦攪拌接合用工具、およびモリブデン耐熱合金の製造方法に関する。   The present invention relates to a molybdenum heat-resistant alloy suitable for a plastic working tool used in a high-temperature environment, particularly a friction stir welding tool, a friction stir welding tool using the same, and a method for producing a molybdenum heat-resistant alloy.

近年、熱間押出用ダイス、継目無製管用ピアサープラグ、射出成形用ホットランナノズル、などの高温環境下で用いられる塑性加工用工具の長寿命化に適する耐熱合金が要求されている。   In recent years, there has been a demand for heat-resistant alloys suitable for extending the life of plastic working tools used in high-temperature environments, such as hot extrusion dies, seamless pipe piercer plugs, and injection molding hot runner nozzles.

特に近年開発の進みつつある摩擦攪拌接合(Friction Stir Welding、以下FSWとも略す)に用いられる回転工具は、摩擦攪拌接合の適用範囲を拡大するため、高温強度および室温硬度の高い材料の開発が進んでいる。   In particular, rotary tools used for friction stir welding (hereinafter also abbreviated as FSW), which are being developed in recent years, have developed materials with high high-temperature strength and room temperature hardness in order to expand the application range of friction stir welding. It is out.

摩擦攪拌接合は、金属部材の接合部に回転工具を押し当て、その摩擦熱により軟化した被接合材を塑性流動させて接合する方法である。摩擦攪拌接合は既に、アルミニウム、マグネシウムなどの低融点、軟質材料の接合において実用化が進み適用範囲が拡大しつつある。しかし現在は、より高融点、硬質な被接合材への適用を図るために、高温強度、耐磨耗性を向上させた実用寿命を有する工具の開発が求められている。   Friction stir welding is a method in which a rotating tool is pressed against a joint portion of a metal member, and a material to be joined softened by the frictional heat is plastically flowed and joined. Friction stir welding has already been put into practical use in joining low melting point, soft materials such as aluminum and magnesium, and its application range is expanding. However, at present, there is a demand for the development of a tool having a practical life with improved high-temperature strength and wear resistance in order to be applied to a material to be bonded having a higher melting point and harder.

その理由として、FSWでは摩擦熱により被接合材を軟化させた際に、接合条件、被接合材による違いがあるものの、一般には工具の温度が被接合材の融点の70%前後にまで上昇することがあるためである。すなわち低融点のアルミニウムではこの温度が約400℃程度であるのに対し、鉄鋼材では1000〜1200℃に達するため、工具材質にはこの温度域においても被接合材を塑性流動させることが出来る高温強度、靭性および耐摩耗性が要求される。これは、FSW、FSJ(Friction Spot Joining、摩擦点接合)および摩擦攪拌応用技術に使用される工具に共通の課題である。   The reason is that in FSW, when the material to be joined is softened by frictional heat, the temperature of the tool generally rises to around 70% of the melting point of the material to be joined, although there are differences depending on the joining conditions and the material to be joined. Because there are things. That is, this temperature is about 400 ° C. for low melting point aluminum, whereas it reaches 1000 to 1200 ° C. for steel materials. Therefore, the tool material has a high temperature that can cause the material to be joined to plastically flow even in this temperature range. Strength, toughness and wear resistance are required. This is a common problem for tools used in FSW, FSJ (Friction Spot Joining) and friction stir application techniques.

その解決策として、比較的入手が容易なMoを主成分として、硬質材料であるTi、Zr、Hfの炭化物を添加し、高温強度を高めたMo合金がある。例えば0.03〜9.5質量%のTi、Zr、Hfの炭化物を添加し、メカニカルアロイング処理により微細組織を有する構造としたモリブデン合金が知られている(特許文献1)。このモリブデン合金は再結晶温度や脆性-延性遷移温度に注目して開発され、メカニカルアロイング処理による微細組織が必須である。しかしながらモリブデンは微細化させることにより非常に酸化性が強くなるため、メカニカルアロイング処理容器の酸素を十分に取り除くことは、工業的レベルでは非常に難しい。   As a solution, there is a Mo alloy in which Mo, which is relatively easy to obtain, is used as a main component and carbides of Ti, Zr, and Hf, which are hard materials, are added to increase the high-temperature strength. For example, a molybdenum alloy in which 0.03 to 9.5% by mass of Ti, Zr, and Hf carbides are added and a microstructure is formed by mechanical alloying is known (Patent Document 1). This molybdenum alloy was developed with a focus on recrystallization temperature and brittle-ductile transition temperature, and a microstructure by mechanical alloying is essential. However, since molybdenum becomes very oxidizable by making it finer, it is very difficult to sufficiently remove oxygen from the mechanical alloying vessel on an industrial level.

また共晶組織を有するモリブデン2相合金があり、Moと添加炭化物の相互拡散反応および共晶反応を利用し良好な組織を得ている(特許文献2)。   Further, there is a molybdenum two-phase alloy having a eutectic structure, and a good structure is obtained by utilizing the mutual diffusion reaction and eutectic reaction between Mo and added carbide (Patent Document 2).

一方で、このMo-炭化物2相合金において、しばしばその反応性から、添加炭化物の異常成長による巨大柱状結晶が生じることがある。例えばTi炭化物の場合、Moに添加されたTi炭化物はMoの固溶体を作り、内部にTiC粒子を有し、その粒子の周りに薄い(Mo、Ti)C固溶体相を生じ、さらにMo相と強固な結合を発生することが、いわゆる有芯構造として公知である(非特許文献1)。しかしながら、TiCはC/Ti=0.5〜0.98の広い非化学量論的組成を持つ。そのため(Mo、Ti)C中間相の組成や厚さが異なり、(Mo、Ti)C中間相同士が接した場合、それぞれの元素の再拡散により安定化するため粒成長を生じることがある。   On the other hand, in this Mo-carbide two-phase alloy, a giant columnar crystal due to abnormal growth of the added carbide often occurs due to its reactivity. For example, in the case of Ti carbide, Ti carbide added to Mo creates a solid solution of Mo, has TiC particles inside, produces a thin (Mo, Ti) C solid solution phase around the particles, and is further strong with the Mo phase. It is known as a so-called cored structure to generate a simple bond (Non-Patent Document 1). However, TiC has a wide non-stoichiometric composition of C / Ti = 0.5-0.98. Therefore, the composition and thickness of the (Mo, Ti) C intermediate phase are different, and when the (Mo, Ti) C intermediate phases are in contact with each other, grain growth may occur due to stabilization by re-diffusion of each element.

このような巨大柱状結晶は強度低下の大きな原因となり、その存在、サイズなどの制御が難しく、素材全体の強度のバラツキにつながる。そのため巨大柱状結晶の形成を防ぐことが工具の実用上強度確保とバラツキの対策として有効な手段となる。なお、Tiと同族元素であるZr、Hfにおいてもその炭化物はTiCと同様な結晶構造ならびに非化学量論的組成を持ち、上記TiCと同じく巨大柱状結晶を生じる。   Such giant columnar crystals cause a significant decrease in strength, and it is difficult to control their presence and size, leading to variations in strength of the entire material. Therefore, preventing the formation of giant columnar crystals is an effective means for ensuring the strength of the tool and for preventing variation. Note that the carbides of Zr and Hf, which are elements similar to Ti, have a crystal structure and non-stoichiometric composition similar to those of TiC, and form giant columnar crystals similar to TiC.

一方、Mo合金以外の耐熱合金としては、高温強度の観点から、PCBN(Polycrystalline Cubic Boron Nitride)などのセラミックスや25%Re−Wがその候補として公知である(特許文献3、4)。しかしながら、PCBNは非常に製法が特殊であるため高価であり、かつ他のセラミックス同様その耐欠損性が低く、欠けが発生しやすいという致命的な欠点がある。一方で25%Re−Wについては金属であるため、靭性は良好であるが耐磨耗性が劣るとともにReが希少であるため入手が困難で高価であるという問題がある。   On the other hand, as heat-resistant alloys other than Mo alloys, ceramics such as PCBN (Polycrystalline Cubic Boron Nitride) and 25% Re-W are known as candidates from the viewpoint of high-temperature strength (Patent Documents 3 and 4). However, PCBN has a fatal defect that it is expensive because it has a very special manufacturing method, and has a low fracture resistance like other ceramics, and chipping easily occurs. On the other hand, since 25% Re-W is a metal, it has good toughness but is inferior in wear resistance and has a problem that it is difficult to obtain and expensive because Re is scarce.

さらに、FSW用工具ではないが、TiCN−Mo系焼結体の性質に関して、TiCNにMoを添加したTiCN基の硬質材料(サーメット)の研究がなされており、非特許文献1では、TiCに比較しTiCNを添加することで、Mo窒化物が生成しにくく、また微粒化することが報告されている。しかしながら、これらの硬質材料はセラミックス基であり、靭性の低さが問題であり、また結合材や焼結助剤としてNi、Co、Moなどその他の金属、炭化物を添加しており、用途も切削工具が主である。   Furthermore, although it is not a tool for FSW, research on a TiCN-based hard material (cermet) in which Mo is added to TiCN has been made regarding the properties of the TiCN-Mo-based sintered body. However, it has been reported that the addition of TiCN makes it difficult for Mo nitrides to form and atomization. However, these hard materials are ceramic-based, and low toughness is a problem, and other metals and carbides such as Ni, Co, and Mo are added as binders and sintering aids. Mainly tools.

特許第3271040号Japanese Patent No. 3271040 特開2008−246553号公報JP 2008-246553 A 特表2003−532543号公報Japanese translation of PCT publication No. 2003-532543 特開2004−358556号公報JP 2004-358556 A

(社)粉体粉末冶金協会編、「粉体粉末便覧」、内田老鶴圃2010年11月10日発行(第1版)291〜295頁(Company) Powder Powder Metallurgy Association, "Powder Powder Handbook", Uchida Otsukuru, November 10, 2010 (first edition), pages 291-295

上記のように、摩擦攪拌接合に関しては、接合対象物は、従来広く用いられていたAlから、近年ではFe系、FeCr系(ステンレス)、Ti系合金、Ni系合金のように、次第に融点の高い金属が用いられるようになってきており、摩擦攪拌接合用の工具には、高融点化に対応した耐塑性変形性、靭性および耐摩耗性、即ち、より高い耐力や硬度が求められている。   As described above, with regard to friction stir welding, the object to be joined is gradually increased in melting point from Al, which has been widely used in the past, to Fe-based, FeCr-based (stainless steel), Ti-based alloy, Ni-based alloy in recent years. Higher metals have come to be used, and tools for friction stir welding are required to have plastic deformation resistance, toughness and wear resistance corresponding to higher melting points, that is, higher proof stress and hardness. .

しかしながら、上記文献の合金は、強度を安定させるための合金組織の制御が困難であるもの、あるいは特殊な製法を要する素材や希少な素材を必要とする高価なものであり、塑性加工用工具材料として実用性を充足していないという問題があった。   However, the alloys described in the above documents are difficult to control the alloy structure in order to stabilize the strength, or are expensive materials that require a special manufacturing method or a rare material, and are a tool material for plastic working. There was a problem that practicality was not satisfied.

本発明は上記課題に鑑みてなされたものであり、その目的は従来よりも加工対象物の高融点化に対応した耐力や硬度等の物性と実用性の双方を充足する、塑性加工用工具用の耐熱合金を提供することにある。   The present invention has been made in view of the above-mentioned problems, and its purpose is for a tool for plastic working that satisfies both physical properties and practicality such as proof stress and hardness corresponding to higher melting point of an object to be processed than before. It is to provide a heat-resistant alloy.

上記した課題を解決するため、本発明者は、Mo-炭化物2相合金、特にその固溶体相に着目し、固溶体相同士の接触による粒成長を抑制することにより、合金の耐力や硬度を改善することが可能か否かを鋭意検討した。   In order to solve the above-mentioned problems, the present inventor focuses on a Mo-carbide two-phase alloy, particularly its solid solution phase, and improves the yield strength and hardness of the alloy by suppressing grain growth due to contact between the solid solution phases. We sought to determine whether this is possible.

その結果、合金成分およびその添加量と固溶体相の粒成長の間には所定の関係があり、これを制御することにより、従来よりも接合対象物の高融点化に対応した耐力や硬度等の物性と実用性の双方を充足するモリブデン耐熱合金を得られることを見出し、本発明を創出するに至った。   As a result, there is a predetermined relationship between the alloy components and the amount of addition and the grain growth of the solid solution phase, and by controlling this, the proof stress, hardness, etc. corresponding to the higher melting point of the object to be joined than before are controlled. The present inventors have found that a molybdenum heat-resistant alloy satisfying both physical properties and practicality can be obtained.

即ち、本発明の第1の態様は、Moを主成分とする第1の相と、Ti、Zr、Hfの少なくとも1つの炭窒化物を主成分とする第2の相と、前記第2の相の周囲に設けられ、MoとTi、Zr、Hfの少なくとも1つの炭窒化物の固溶体を有する第3の相と、を有し、残部が不可避不純物であることを特徴とするモリブデン耐熱合金である。   That is, the first aspect of the present invention includes a first phase mainly composed of Mo, a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf, and the second phase. And a third phase having a solid solution of Mo and at least one carbonitride of Ti, Zr, and Hf provided around the phase, and the remainder being an inevitable impurity. is there.

本発明の第2の態様は、第1の態様に記載の摩擦攪拌接合用工具の表面に、周期律表IVa、Va、VIa、IIIb族元素およびC以外のIVb族元素よりなる群から選択される少なくとも1種以上の元素、またはこれら元素群から選択される少なくとも1種以上の元素の炭化物、窒化物あるいは炭窒化物を含む被膜層を有することを特徴とする摩擦攪拌接合用工具である。   In a second aspect of the present invention, the surface of the friction stir welding tool according to the first aspect is selected from the group consisting of periodic table IVa, Va, VIa, group IIIb elements and group IVb elements other than C. A friction stir welding tool comprising a coating layer containing carbide, nitride, or carbonitride of at least one element selected from the group consisting of at least one element or at least one element selected from these element groups.

本発明の第3の態様は、第2の態様に記載の摩擦攪拌接合用工具を有することを特徴とする摩擦攪拌装置である。   According to a third aspect of the present invention, there is provided a friction stirrer comprising the friction stir welding tool according to the second aspect.

本発明の第4の態様は、Mo粉末と、炭窒化物粉末を混合する混合工程と、前記混合工程により得られた混合粉を室温中で圧縮成形する成形工程と、前記成形工程により得られた成形体を少なくとも水素と窒素を含む雰囲気にて1600℃以上、2000℃以下で加熱する焼結工程と、前記焼結工程により得られた焼結体を不活性雰囲気にて熱間等方圧加圧する加圧工程と、を具える、第1の態様に記載のモリブデン耐熱合金を製造する製造方法である。   The fourth aspect of the present invention is obtained by the mixing step of mixing the Mo powder and the carbonitride powder, the forming step of compression-molding the mixed powder obtained by the mixing step at room temperature, and the forming step. A sintering process in which the molded body is heated in an atmosphere containing at least hydrogen and nitrogen at 1600 ° C. or more and 2000 ° C. or less, and the sintered body obtained by the sintering process is subjected to hot isostatic pressure in an inert atmosphere. It is a manufacturing method which manufactures the molybdenum heat-resistant alloy as described in a 1st aspect provided with the pressurization process which pressurizes.

本発明によれば、従来よりも加工対象物の高融点化に対応した耐力や硬度等の物性と実用性の双方を充足する、塑性加工用工具用の耐熱合金を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the heat-resistant alloy for tools for plastic working which satisfies both physical properties, such as proof stress and hardness corresponding to the high melting point of a workpiece, and practicality compared with the former can be provided.

Mo−TiC二元系状態図を示す図である。It is a figure which shows a Mo-TiC binary system phase diagram. MoにTiCを添加した合金中の各相の模式図である。It is a schematic diagram of each phase in the alloy which added TiC to Mo. 本発明のモリブデン耐熱合金中の各相の模式図である。It is a schematic diagram of each phase in the molybdenum heat-resistant alloy of this invention. 本発明のモリブデン耐熱合金中の炭窒化チタン粒の粒径分布を示す図である。It is a figure which shows the particle size distribution of the titanium carbonitride grain in the molybdenum heat-resistant alloy of this invention. 本発明のモリブデン耐熱合金中の炭窒化チタン粒の粒径分布を示す図である。It is a figure which shows the particle size distribution of the titanium carbonitride grain in the molybdenum heat-resistant alloy of this invention. 本発明のFSW用工具の製造方法を示すフローチャートである。It is a flowchart which shows the manufacturing method of the tool for FSW of this invention. 本発明のFSW用工具101を示す側面図である。It is a side view which shows the tool 101 for FSW of this invention. 本発明の実施例に係る摩擦攪拌接合工具を形成するモリブデン耐熱合金の断面の拡大写真を模した図であって、異なる相ごとに着色した図である。It is the figure which modeled the enlarged photograph of the cross section of the molybdenum heat-resistant alloy which forms the friction stir welding tool which concerns on the Example of this invention, Comprising: It is the figure colored for every different phase. 本発明の実施例に係る摩擦攪拌接合工具を形成するモリブデン耐熱合金のX線回折結果を示す図である。It is a figure which shows the X-ray-diffraction result of the molybdenum heat-resistant alloy which forms the friction stir welding tool which concerns on the Example of this invention. 表1の比較例4の電子顕微鏡写真である。5 is an electron micrograph of Comparative Example 4 in Table 1. 表1の本発明3の電子顕微鏡写真である。It is an electron micrograph of the present invention 3 of Table 1.

以下、図面を参照して本発明に好適な実施形態を詳細に説明する。   DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, exemplary embodiments suitable for the invention will be described in detail with reference to the drawings.

<モリブデン耐熱合金組成>
まず、本発明の摩擦攪拌接合用工具(塑性加工用工具)に用いられるモリブデン耐熱合金の組成について説明する。
<Molybdenum heat-resistant alloy composition>
First, the composition of the molybdenum heat-resistant alloy used in the friction stir welding tool (plastic working tool) of the present invention will be described.

本発明の摩擦攪拌接合用工具に用いられるモリブデン耐熱合金は、Moを主成分とする第1の相と、Ti、Zr、Hfの少なくとも1つの炭窒化物を主成分とする第2の相と、前記第2の相の周囲に設けられ、MoとTi、Zr、Hfの少なくとも1つの炭窒化物を含む固溶体を有する第3の相とを有し、残部が不可避不純物であることを特徴とするモリブデン耐熱合金である。   The molybdenum heat-resistant alloy used in the friction stir welding tool of the present invention includes a first phase mainly composed of Mo and a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf. And a third phase having a solid solution containing Mo and at least one carbonitride of Ti, Zr, and Hf provided around the second phase, the balance being inevitable impurities Molybdenum heat-resistant alloy.

以下、各相および各相を構成する材料について説明する。
<第1の相>
第1の相はMoを主成分とする相である。ここでいう主成分とは最も含有量が多い成分であることを意味する(以下同様)。
Hereinafter, each phase and materials constituting each phase will be described.
<First phase>
The first phase is a phase mainly composed of Mo. The main component here means a component having the highest content (the same applies hereinafter).

具体的には、第1の相は例えばMoと不可避不純物で構成されるが、後述する炭窒化物の含有量によっては、第1の相に炭窒化物を構成する元素が固溶している場合もある。   Specifically, the first phase is composed of, for example, Mo and inevitable impurities, but depending on the content of carbonitride described later, the elements constituting the carbonitride are in solid solution in the first phase. In some cases.

第1の相におけるMoは高融点、高硬度でかつ高温における強度に優れ、耐熱合金に金属としての物性をもたせるために、必須である。   Mo in the first phase has a high melting point, high hardness, and excellent strength at high temperatures, and is essential for imparting physical properties as a metal to the heat-resistant alloy.

合金中のMoの含有量は、後述する炭窒化物の含有率との関係で決まるが、耐熱合金に金属としての物性をもたせるためには50質量%以上であるのが好ましい。   The content of Mo in the alloy is determined by the relationship with the content of carbonitride described later, but is preferably 50% by mass or more in order to give the heat-resistant alloy physical properties.

<第2の相>
第2の相は、Ti、Zr、Hfの少なくとも1つの炭窒化物を主成分とする相であり、具体的には、例えば上記した炭窒化物と不可避不純物で構成される。
<Second phase>
The second phase is a phase mainly composed of at least one of Ti, Zr, and Hf carbonitride, and specifically includes, for example, the above-described carbonitride and inevitable impurities.

第2の相におけるTi、Zr、Hfの炭窒化物は、Moに添加することにより、後述するように、結晶粒が微細化され硬度と高温での0.2%耐力を高めることができるため、必須である。   Since the carbonitrides of Ti, Zr, and Hf in the second phase are added to Mo, as will be described later, the crystal grains are refined and the hardness and 0.2% proof stress at high temperature can be increased. Is essential.

なお、炭窒化物の代表的なものとしてはTiCNが挙げられるが、TiCNの組成としては、例えばTiC1−x(x=0.3〜0.7)となるものが挙げられ、具体的にはTiC0.30.7、TiC0.50.5、TiC0.70.3などが挙げられる。 A typical carbonitride includes TiCN, and the composition of TiCN includes, for example, TiC x N 1-x (x = 0.3 to 0.7). thereof include TiC 0.3 N 0.7, TiC 0.5 N 0.5, like TiC 0.7 N 0.3.

この中で代表的なものとしては、TiC0.50.5が知られているが、その他の組成の炭窒化チタン、炭窒化ジルコニウム、炭窒化ハフニウムも、TiC0.50.5と同様に結晶粒の微細化の効果が得られる。 Among them, TiC 0.5 N 0.5 is known as a typical one, but titanium carbonitride, zirconium carbonitride, and hafnium carbonitride having other compositions are also TiC 0.5 N 0.5. The effect of crystal grain refinement can be obtained in the same manner as above.

なお、合金中の炭窒化物(例えばTiCN)の含有量が5質量%未満の場合、室温硬度、高温での0.2%耐力を高くする効果が得られず、50質量%を超える場合、焼結性が悪くなり十分な密度が得られず、必要な機械的強度が得られなくなる。   In addition, when the content of carbonitride (for example, TiCN) in the alloy is less than 5% by mass, the effect of increasing the 0.2% proof stress at room temperature hardness and high temperature cannot be obtained, and when the content exceeds 50% by mass, The sinterability deteriorates and a sufficient density cannot be obtained, and the required mechanical strength cannot be obtained.

そのため、合金中のTiCNの含有量は5質量%以上50質量%以下であることが好ましく、より好ましくは、10質量%以上40質量%以下、さらに好ましくは30質量%以上40質量%以下とするのが良い。   Therefore, the content of TiCN in the alloy is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 30% by mass or more and 40% by mass or less. Is good.

<第3の相>
第3の相は第2の相の周囲に形成される層であり、第1の相のMoと第2の相の炭窒化物との固溶体を主成分とし、これと不可避不純物で構成される。
<Third phase>
The third phase is a layer formed around the second phase, and is mainly composed of a solid solution of Mo of the first phase and carbonitride of the second phase, and is composed of this and inevitable impurities. .

ここで、図1〜図3を参照して本発明のMo耐熱材料に炭窒化物を添加したことによる効果を、炭化物を添加した場合と比較して説明する。ここではセラミックスとしてTiを例にして説明するが、Zr、Hfを用いた場合の効果も同様である。   Here, with reference to FIGS. 1-3, the effect by having added carbonitride to Mo heat resistant material of this invention is demonstrated compared with the case where a carbide is added. Here, Ti will be described as an example of ceramics, but the effect of using Zr and Hf is the same.

前述のようにMoにTi炭化物を添加した場合、添加されたTi炭化物は添加炭化物の相互拡散反応および共晶反応(図1参照)により図2に示すように、Moの固溶体を作り、内部にTi炭化物粒子を有し、その粒子の周囲に(Mo、Ti)C固溶体を生じる。   As described above, when Ti carbide is added to Mo, the added Ti carbide forms a solid solution of Mo as shown in FIG. 2 by the interdiffusion reaction and eutectic reaction of the added carbide (see FIG. 1). It has Ti carbide particles and produces a (Mo, Ti) C solid solution around the particles.

この際、前述のように、TiCはC/Ti=0.5〜0.98の広い非化学量論的組成を持つ。そのため、(Mo、Ti)C中間相の組成や厚さは一定にはならず、組成や厚さの異なる(Mo、Ti)C中間相同士が接した場合、それぞれの元素の再拡散により安定化するため粒成長を生じ、巨大柱状結晶が形成されて強度低下を引き起こす恐れがある。   At this time, as described above, TiC has a wide non-stoichiometric composition of C / Ti = 0.5 to 0.98. Therefore, the composition and thickness of the (Mo, Ti) C intermediate phase are not constant, and when (Mo, Ti) C intermediate phases with different compositions and thickness are in contact with each other, they are stabilized by re-diffusion of the respective elements. Therefore, there is a possibility that grain growth occurs and a giant columnar crystal is formed, causing a decrease in strength.

一方で、図3に示すように、MoにTi炭窒化物を添加した場合も、Ti炭窒化物(TiCN)はMoとの固溶体(第3の相)を生じ、内部にTi炭窒化物(第2の相)を有し、その粒子の周囲には(Mo、Ti)C固溶体を生じる。   On the other hand, as shown in FIG. 3, when Ti carbonitride is added to Mo, Ti carbonitride (TiCN) produces a solid solution (third phase) with Mo, and Ti carbonitride ( A (Mo, Ti) C solid solution is formed around the particles.

しかしながら、この構造の場合、図3から明らかなように、Ti炭化物を添加した場合と比較してMoとTi炭化物の接触機会が減少する。   However, in the case of this structure, as is apparent from FIG. 3, the contact opportunity between Mo and Ti carbide is reduced as compared with the case where Ti carbide is added.

さらに、Moは窒素との親和力が炭素との親和力よりも小さいため、Ti窒化物はTi炭化物に比較しMoと反応しにくく、さらに(Mo、Ti)CN固溶体(第3の相)同士の反応も(Mo、Ti)C固溶体相に比較し減少する。   Furthermore, since Mo has a smaller affinity for nitrogen than that for carbon, Ti nitrides are less likely to react with Mo than Ti carbides, and the reaction between (Mo, Ti) CN solid solutions (third phase). Also decreases compared to the (Mo, Ti) C solid solution phase.

そのため、Moに炭窒化物を添加した場合、炭化物を添加した場合と比較して、固溶体相に起因する粒成長が生じにくくなり、その結果、炭窒化物は微細に析出することとなる。そのためモリブデン耐熱合金の組織は微細化され、強度、靭性が向上する。
以上が炭窒化物を添加したことによる効果である。
Therefore, when carbonitride is added to Mo, grain growth caused by the solid solution phase is less likely to occur than when carbide is added, and as a result, carbonitride is finely precipitated. Therefore, the structure of the molybdenum heat-resistant alloy is refined, and the strength and toughness are improved.
The above is the effect obtained by adding carbonitride.

<不可避不純物>
本発明に係るFSW用工具を形成するモリブデン耐熱合金は、上記した必須の成分に加え、不可避不純物を含む場合がある。
<Inevitable impurities>
The molybdenum heat-resistant alloy forming the FSW tool according to the present invention may contain inevitable impurities in addition to the above-described essential components.

不可避不純物としては、Fe、Ni、Cr、などの金属成分や、C、N、Oなどがある。   Inevitable impurities include metal components such as Fe, Ni, and Cr, and C, N, and O.

<TiCNの粒径>
次に、本発明の摩擦攪拌接合用工具を形成する焼結後のモリブデン耐熱合金中の炭窒化物の粒径(第2の相の粒径)について説明する。
<TiCN particle size>
Next, the particle size (second phase particle size) of carbonitride in the sintered molybdenum heat-resistant alloy that forms the friction stir welding tool of the present invention will be described.

ここでは炭窒化物としてTiCNを例に説明するが、炭窒化ジルコニウム、炭窒化ハフニウム等も同様である。   Here, TiCN is described as an example of carbonitride, but the same applies to zirconium carbonitride, hafnium carbonitride, and the like.

本発明の摩擦攪拌接合用工具を形成する焼結後のモリブデン耐熱合金中のTiCNの粒径は、平均粒径が0.3μm以上、10μm以下であるのが好ましい。これは、以下の理由によるものである。   The particle size of TiCN in the sintered heat-resistant molybdenum alloy forming the friction stir welding tool of the present invention is preferably an average particle size of 0.3 μm or more and 10 μm or less. This is due to the following reason.

まず、平均粒径を0.3μm以上とする理由について説明する。
仮に、平均粒径を0.3μmよりも小さくする場合、配合するTiCN粉末の平均粒径を0.3μmより小さくする必要がある。しかし、このような微粒子は一般的に凝集し易くなる傾向があり、凝集2次粒子は焼結により顕著な粗大粒を形成し易くなり、また気孔の生成も促し易い。このような顕著な粗大粒子を形成させないためには、焼結温度を低下させる必要があるが、焼結温度の低下は焼結体密度の低下を引き起こしてしまう。
そのため、TiCNの平均粒径は0.3μm以上であるのが好ましい。
First, the reason why the average particle size is 0.3 μm or more will be described.
If the average particle size is smaller than 0.3 μm, the average particle size of the TiCN powder to be blended needs to be smaller than 0.3 μm. However, such fine particles generally tend to be easily aggregated, and the aggregated secondary particles are liable to form remarkable coarse particles by sintering and also facilitate the generation of pores. In order not to form such remarkable coarse particles, it is necessary to lower the sintering temperature. However, the lowering of the sintering temperature causes a decrease in the density of the sintered body.
Therefore, the average particle size of TiCN is preferably 0.3 μm or more.

次に、平均粒径を10μm以下とする理由について説明する。
仮にモリブデン耐熱合金中のTiCNの平均粒径を10μmよりも大きくする場合、粗粒のTiCNが焼結を阻害して焼結歩留まりが極端に悪くなり、工業的とはいえなくなる恐れがある。さらに焼結できたとしても粗粒のTiCN粒子が破壊の起点となって、機械的強度を低下させる恐れがある。
そのため、TiCNの平均粒径は10μm以下であるのが好ましい。
Next, the reason why the average particle size is 10 μm or less will be described.
If the average particle size of TiCN in the molybdenum heat-resistant alloy is made larger than 10 μm, coarse TiCN inhibits the sintering, resulting in extremely poor sintering yield and may not be industrial. Further, even if sintering is possible, coarse TiCN particles may be the starting point of fracture, which may reduce the mechanical strength.
Therefore, the average particle size of TiCN is preferably 10 μm or less.

また、焼結体の密度上昇と均一性の確保という観点からは、TiCNの平均粒径は0.3μm〜6μmであることがより好ましい。   Further, from the viewpoint of increasing the density of the sintered body and ensuring uniformity, the average particle size of TiCN is more preferably 0.3 μm to 6 μm.

なお、詳細は後述するが、ここでいう平均粒径とは、線インターセプト法で求めた値のことである。   In addition, although mentioned later for details, the average particle diameter here is the value calculated | required by the line intercept method.

また、合金中のTiCN粒は、図4に示すように、3.0〜5.0μmの粒子の個数割合が合金中のTiCN粒全体の40−60%の割合であるのが好ましい。これは、前述のように、TiCN粒の平均粒径は0.3〜6μmであるのが好ましいが、ひとつのほぼ正規分布の粒度を示している場合、粒度分布がブロード過ぎると焼結体組織の不均一性、即ち焼結体部位に関し特性の不均一性につながる可能性があるためであり、一方、非常に均一な粒度の粉末は得られ難く、製造コストの面でデメリットがあるためである。   Moreover, as for the TiCN grain in an alloy, as shown in FIG. 4, it is preferable that the number ratio of the particle | grains of 3.0-5.0 micrometers is a ratio of 40-60% of the whole TiCN grain in an alloy. As described above, it is preferable that the average particle size of the TiCN particles is 0.3 to 6 μm. However, when the particle size distribution is too broad when the particle size distribution is too broad, This is because there is a possibility that it may lead to non-uniformity of the properties of the sintered body, that is, it is difficult to obtain a powder with a very uniform particle size, and there is a disadvantage in terms of manufacturing cost. is there.

さらに、TiCN粒は、微粒と粗粒を織り交ぜることにより、添加の効果をより高めることができる。具体的には、図5に示すように、粒径が1.5〜3.5μmの粒子の個数割合が合金中のTiCN粒全体の20−40%の割合、5.0〜7.0μmの粒子の個数割合が合金中のTiCN粒全体の10−30%の割合であるのがより好ましい。このような分布とすることにより、微粒側の粒径1.5μm〜3.5μmのTiCN粒は、主としてMoの粒界に介在することにより、Moの粒界強度を高める効果に寄与する(効果A)。一方、粗粒側の粒径5.0〜7.0μmのTiCN粒は、モリブデン耐熱合金のバルク全体の硬度を高める効果に寄与する(効果B)。   Furthermore, the effect of addition can be further enhanced by interweaving fine grains and coarse grains with TiCN grains. Specifically, as shown in FIG. 5, the number ratio of particles having a particle diameter of 1.5 to 3.5 μm is a ratio of 20 to 40% of the whole TiCN grains in the alloy, and is 5.0 to 7.0 μm. More preferably, the number ratio of the particles is 10-30% of the total TiCN grains in the alloy. With such a distribution, TiCN grains having a grain size of 1.5 μm to 3.5 μm on the fine grain side mainly contribute to the effect of increasing the grain boundary strength of Mo by intervening in the grain boundary of Mo (effect A). On the other hand, TiCN grains having a grain size of 5.0 to 7.0 μm on the coarse grain side contribute to the effect of increasing the hardness of the entire bulk of the molybdenum heat-resistant alloy (effect B).

なお、粒径が1.5−3.5μmの粒子の個数割合が20%より低いと、粗粒の比率が高くなるため、効果Aが得られ難く、40%より高いと、微粒の比率が高すぎ、効果Bが得られ難いため、好ましくない。   If the ratio of the number of particles having a particle size of 1.5 to 3.5 μm is lower than 20%, the ratio of coarse particles becomes high, so that the effect A is difficult to be obtained. Since it is too high and it is difficult to obtain the effect B, it is not preferable.

また、粒径が5.0-7.0μmの粒子の個数割合が10%より低いと、粗粒の比率が低くなるため、効果Bが得られ難く、30%より高いと、粗粒の比率が高くなり、効果Aが得られ難いため、好ましくない。   Further, if the number ratio of the particles having a particle size of 5.0-7.0 μm is lower than 10%, the ratio of the coarse particles becomes low, so that the effect B is difficult to be obtained. Increases, and it is difficult to obtain the effect A, which is not preferable.

<物性>
次に、本発明の摩擦攪拌接合用工具を形成するモリブデン耐熱合金の物性について説明する。
<Physical properties>
Next, the physical properties of the molybdenum heat-resistant alloy forming the friction stir welding tool of the present invention will be described.

本発明のモリブデン耐熱合金の強度としては、1200℃における0.2%耐力が400MPa以上、好ましくは600MPa以上、かつ20℃におけるビッカース硬度(室温硬度)が400Hv以上、好ましくは600Hv以上である。   As the strength of the molybdenum heat-resistant alloy of the present invention, the 0.2% proof stress at 1200 ° C. is 400 MPa or more, preferably 600 MPa or more, and the Vickers hardness (room temperature hardness) at 20 ° C. is 400 Hv or more, preferably 600 Hv or more.

モリブデン耐熱合金をこのような物性にすることにより、モリブデン耐熱合金を例えばFe系、FeCr系、Ti系用等の摩擦攪拌接合部材のような、高融点、高強度が要求される耐熱部材に適用することができる。   By making molybdenum heat-resistant alloys such physical properties, molybdenum heat-resistant alloys are applied to heat-resistant members that require high melting points and high strength, such as friction stir welding members for Fe-based, FeCr-based, Ti-based, etc. can do.

なお、本発明がモリブデン「耐熱」合金であるにも関わらず、室温硬度を条件にしているのは、以下の理由によるものである。   In spite of the fact that the present invention is a molybdenum “heat-resistant” alloy, the room temperature hardness is required for the following reasons.

本発明のモリブデン耐熱合金を摩擦攪拌接合用工具として用いる場合、工具の摩耗量が工具材料の硬度と密接な関係にあり、硬度が高いほど工具摩耗量を少なくできる効果がある。摩擦攪拌接合の場合、ツールを挿入する際に工具への高い負荷が生じるため、挿入時の摩耗が顕著に現れる。挿入時はまだ工具もワークも発熱が少なく、両者の温度も高くはなっていないため、工具の摩耗量は、室温の硬度に依存することとなる。   When the molybdenum heat-resistant alloy of the present invention is used as a friction stir welding tool, the wear amount of the tool is closely related to the hardness of the tool material, and the higher the hardness, the more effective the tool wear amount can be reduced. In the case of friction stir welding, since a high load is applied to the tool when the tool is inserted, wear during insertion appears significantly. At the time of insertion, both the tool and the work still generate little heat, and the temperature of both is not high. Therefore, the wear amount of the tool depends on the hardness at room temperature.

また、本発明のモリブデン耐熱合金は、摩擦攪拌接合用工具そのものとして使用される場合もあるが、多くの場合は摩擦攪拌接合用工具母材として使用され、周期律表IVa、Va、VIa、IIIb族元素およびC以外のIVb族元素よりなる群から選択される少なくとも1種以上の元素、またはこれら元素群から選択される少なくとも1種以上の元素の炭化物、窒化物あるいは炭窒化物を含む被膜が表面に被覆され工具とされる。ここで、実際に工具として使用する場合、まず室温にて工具を接合対象材料に強く押し込みながら回転させ、摩擦熱により接合対象物の温度を上昇させる。よって、回転初期の母材の変形、破壊また母材と被覆膜との剥離がないように、母材の室温硬度が高いことが必要である。
以上がモリブデン耐熱合金の条件である。
The molybdenum heat-resistant alloy of the present invention may be used as a friction stir welding tool itself, but in many cases it is used as a friction stir welding tool base material, and the periodic table IVa, Va, VIa, IIIb A coating containing at least one element selected from the group consisting of Group IV elements and Group IVb elements other than C, or a carbide, nitride or carbonitride of at least one element selected from these element groups The surface is coated and used as a tool. Here, when actually used as a tool, first, the tool is rotated while being strongly pushed into the material to be joined at room temperature, and the temperature of the object to be joined is increased by frictional heat. Therefore, it is necessary that the base material has a high room temperature hardness so that the base material is not deformed or broken at the initial stage of rotation, or the base material and the coating film are not separated.
The above is the condition of the molybdenum heat-resistant alloy.

<製造方法>
次に、本発明のモリブデン耐熱合金およびそれを用いた摩擦攪拌接合用工具の製造方法について、図6を参照して説明する。
<Manufacturing method>
Next, a molybdenum heat-resistant alloy of the present invention and a method for producing a friction stir welding tool using the same will be described with reference to FIG.

本発明のモリブデン耐熱合金およびそれを用いた摩擦攪拌接合用工具の製造方法については、上記した条件を満たす摩擦攪拌接合用工具が製造できるものであれば、特に限定されるものではないが、以下のような方法を例示することができる。   The method for manufacturing the molybdenum heat-resistant alloy of the present invention and the friction stir welding tool using the same is not particularly limited as long as the friction stir welding tool that satisfies the above conditions can be manufactured. Examples of such a method can be given.

まず、原料粉末を所定の比率で混合して混合粉末を生成する(図6のS1)。   First, the raw material powder is mixed at a predetermined ratio to generate a mixed powder (S1 in FIG. 6).

原料としては、Mo粉末およびTiCN粉末(または炭窒化チタン、炭窒化ジルコニウム、炭窒化ハフニウム等の炭窒化物粉末)が挙げられるが、以下、各粉末の条件について、簡単に説明する。   Examples of the raw material include Mo powder and TiCN powder (or carbonitride powder such as titanium carbonitride, zirconium carbonitride, hafnium carbonitride, etc.). The conditions of each powder will be briefly described below.

Mo粉末は純度99.99質量%以上、Fsss(Fisher Sub-Sieve Sizer)平均粒径3.5〜5.0μmのものを用いるのが好ましい。   It is preferable to use Mo powder having a purity of 99.99% by mass or more and an Fss (Fisher Sub-Sieve Sizer) average particle size of 3.5 to 5.0 μm.

なお、ここでいうMo粉末純度とは、JIS H 1404記載のモリブデン材料の分析方法により得たものであり、Al、Ca、Cr、Cu、Fe、Mg、Mn、Ni、Pb、Si、Snの値を除いた金属純分を意味する。   In addition, Mo powder purity here is obtained by the analysis method of molybdenum material described in JIS H 1404, and includes Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, and Sn. It means the pure metal part excluding the value.

TiCN粉末は、純度99.9%以上、Fsss平均粒径0.1〜10.0μmのもの用いるのが好ましい。   The TiCN powder is preferably used with a purity of 99.9% or more and an Fsss average particle size of 0.1 to 10.0 μm.

なお、ここでいうTiCN粉末の純度とは、Al、Ca、Cr、Cu、Fe、Mg、Mn、Ni、Si、Snを除いた純分を意味する。   The purity of the TiCN powder referred to here means a pure component excluding Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, and Sn.

また、粉末の混合に用いる装置や方法については特に限定されることはなく、例えば、乳鉢、V型ミキサー、ボールミルなど公知の混合機を使用することができる。   Moreover, the apparatus and method used for mixing the powder are not particularly limited, and for example, a known mixer such as a mortar, a V-type mixer, or a ball mill can be used.

次に、得られた混合粉末を圧縮成形し、成形体を形成する(図6のS2)。   Next, the obtained mixed powder is compression molded to form a molded body (S2 in FIG. 6).

圧縮成形に用いる装置は特に限定されるものではなく、一軸式プレス機やCIP(Cold Isostatic Pressing)など公知の成形機を使用すればよい。圧縮の際の条件としては、圧縮の際の温度は室温(20℃)でよい。   The apparatus used for compression molding is not particularly limited, and a known molding machine such as a uniaxial pressing machine or CIP (Cold Isostatic Pressing) may be used. As a condition at the time of compression, the temperature at the time of compression may be room temperature (20 ° C.).

一方、成形圧は1〜3ton/cmであるのが好ましい。これは、成形圧が1ton/cm未満の場合は成形体が十分な密度を得られず、また、3ton/cmを超えると、圧縮装置と金型が大型化し、コスト面で不利になるためである。 On the other hand, the molding pressure is preferably 1 to 3 ton / cm 2 . If this is the molding pressure is less than 1 ton / cm 2 not obtained molded body a sufficient density, also exceeds 3 ton / cm 2, compression system and the mold is large, which is disadvantageous in cost Because.

次に、得られた成形体を加熱し、焼結する(図6のS3)。   Next, the obtained molded body is heated and sintered (S3 in FIG. 6).

具体的には、少なくとも水素あるいは窒素を含む雰囲気(例えばH、H−Ar、H−N混合雰囲気、減圧N雰囲気等)にて1600℃以上、2000℃以下で加熱するのが好ましい。 Specifically, heating is performed at 1600 ° C. or more and 2000 ° C. or less in an atmosphere containing at least hydrogen or nitrogen (for example, H 2 , H 2 —Ar, H 2 —N 2 mixed atmosphere, reduced pressure N 2 atmosphere, etc.). preferable.

これは、加熱温度が1600℃未満の場合、焼結不十分となり焼結体の密度が低くなるためであり、また、加熱温度が2000℃より高いと、TiCNの分解が進行することにより巨大柱状結晶粒の成長へと至り、その結果モリブデン耐熱合金の強度が低下してしまうためである。そのため、焼結する際には、1600℃以上、2000℃以下で焼結するのが好ましい。また、水素あるいは窒素を少なくとも含む雰囲気である理由は、水素は原料粉末が含む酸素の還元作用があり、また窒素は焼結中の脱窒を防ぐ効果があるためである。なお、焼結時の圧力は大気圧で可能であるが、これに限定されず、加圧、減圧のいずれでも焼結可能である。   This is because when the heating temperature is less than 1600 ° C., the sintering is insufficient and the density of the sintered body becomes low, and when the heating temperature is higher than 2000 ° C., the decomposition of TiCN proceeds to cause a huge columnar shape. This is because crystal grains are grown, and as a result, the strength of the molybdenum heat-resistant alloy is lowered. Therefore, when sintering, it is preferable to sinter at 1600 degreeC or more and 2000 degrees C or less. The reason for the atmosphere containing at least hydrogen or nitrogen is that hydrogen has an action of reducing oxygen contained in the raw material powder, and nitrogen has an effect of preventing denitrification during sintering. The pressure at the time of sintering can be atmospheric pressure, but is not limited to this, and sintering can be performed by either pressurization or reduced pressure.

次に、得られた焼結体の相対密度が95%程度であった場合には、不活性雰囲気にて熱間等方圧加圧(Hot Isostatic Pressing 以降HIPとも呼ぶ)することが好ましい。(図6のS4)。ただし、焼結工程で相対密度が96%以上となっていれば、HIPを省略しても室温硬度や高温での0.2%耐力を低下させることはほとんどない。   Next, when the relative density of the obtained sintered body is about 95%, it is preferable to perform hot isostatic pressing (hereinafter also referred to as HIP) in an inert atmosphere. (S4 in FIG. 6). However, if the relative density is 96% or more in the sintering process, even if HIP is omitted, the room temperature hardness and the 0.2% yield strength at high temperatures are hardly lowered.

HIPを行う際の具体的な加圧条件としては、温度1400〜1800℃、圧力152.0〜253.3MPaの不活性雰囲気で、HIP処理を行うのが好ましい。これは、この範囲を下回ると密度が上がらなくなり、上回ると大型装置が必要となり製造コストに影響するためである。   As specific pressurizing conditions for performing HIP, it is preferable to perform the HIP treatment in an inert atmosphere at a temperature of 1400 to 1800 ° C. and a pressure of 152.0 to 253.3 MPa. This is because the density cannot be increased below this range, and if it exceeds this range, a large apparatus is required, which affects the manufacturing cost.

このようにして得られたFSW用工具の素材は、切削工程、研削・研磨工程等の加工工程を経て、摩擦攪拌接合工具が作製される。   The material for the FSW tool thus obtained is subjected to processing steps such as a cutting step, a grinding / polishing step, etc., and a friction stir welding tool is produced.

以上が本発明のモリブデン耐熱合金とそれを用いた摩擦攪拌接合用工具の製造方法である。   The above is the molybdenum heat-resistant alloy of the present invention and the method for producing a friction stir welding tool using the same.

<FSW用工具>
本発明のFSWを形成するモリブデン耐熱合金は、上記の構成を有するものであるが、ここで、本発明のモリブデン耐熱合金を用いた摩擦攪拌接合用工具の構成について、図7を参照して簡単に説明する。
<Tool for FSW>
The molybdenum heat-resistant alloy forming the FSW of the present invention has the above-described configuration. Here, the configuration of the friction stir welding tool using the molybdenum heat-resistant alloy of the present invention is simply described with reference to FIG. Explained.

図7に示すように、摩擦攪拌接合用工具101は、接合装置の図示しない主軸と連結されるシャンク102と、接合時に接合対象物の表面と接触するショルダー部103と、接合時に接合対象物に挿入されるピン部104を有している。   As shown in FIG. 7, the friction stir welding tool 101 includes a shank 102 connected to a main shaft (not shown) of the joining device, a shoulder portion 103 that comes into contact with the surface of the joining object at the time of joining, and a joining object at the time of joining. It has the pin part 104 inserted.

このうち、少なくともショルダー103とピン部104の母材は、本発明に係るモリブデン耐熱合金で形成される。   Among these, at least the base material of the shoulder 103 and the pin portion 104 is formed of the molybdenum heat-resistant alloy according to the present invention.

また、摩擦攪拌接合用工具が使用中の温度によって酸化、また接合対象物と溶着することのないように、モリブデン耐熱合金の表面に周期律表IVa、Va、VIa、IIIb族元素およびC以外のIVb族元素よりなる群から選択される少なくとも1種以上の元素、またはこれら元素群から選択される少なくとも1種以上の元素の炭化物、窒化物あるいは炭窒化物を含む被膜が表面に被覆されるのが好ましい。被膜層の厚さは、1〜20μmが好ましい。被膜層の厚さが1μm未満の場合は、被膜層を設けたことによる効果が期待できない。一方で、被膜層の厚さが20μm以上の場合は、過大な応力が生じ膜が剥離する恐れがあるため、極端に歩留まりが悪くなる可能性がある。   In addition, other than periodic elements IVa, Va, VIa, IIIb elements and C on the surface of the molybdenum heat-resistant alloy so that the friction stir welding tool is not oxidized or welded to the object to be welded due to the temperature during use. The surface is coated with at least one element selected from the group consisting of group IVb elements or a carbide, nitride or carbonitride of at least one element selected from these elements. Is preferred. The thickness of the coating layer is preferably 1 to 20 μm. When the thickness of the coating layer is less than 1 μm, the effect of providing the coating layer cannot be expected. On the other hand, when the thickness of the coating layer is 20 μm or more, an excessive stress may be generated and the film may be peeled off, so that the yield may be extremely deteriorated.

このような被膜(コーティング層)としては、TiC、TiN、TiCN、ZrC、ZrN、ZrCN、VC、VN、VCN、CrC、CrN、CrCN、TiAlN、TiSiN、TiCrN、並びに少なくともこれらの内の1層以上を含む多層膜を有するものが挙げられる。ここで、コーティング層の各元素の組成比率は任意に設定できる。上記TiCNも本願発明に記載のTiC1−x(x=0.3〜0.7)のX値に限定されるものではない。 As such a coating (coating layer), TiC, TiN, TiCN, ZrC, ZrN, ZrCN, VC, VN, VCN, CrC, CrN, CrCN, TiAlN, TiSiN, TiCrN, and at least one of these layers And having a multilayer film containing Here, the composition ratio of each element of the coating layer can be arbitrarily set. The TiCN is not limited to the X value of TiC x N 1-x (x = 0.3 to 0.7) described in the present invention.

コーティング層の形成方法は、特に限定されることなく、公知の方法で被膜形成できる。代表的な方法として、アークイオンプレーティングやスパッタリングなどのPVD(Physical Vapor Deposition)処理、化学反応によりコーティングするCVD(Chemical Vapor Deposition)処理、ガス状元素をプラズマにより分解、イオン化しコーティングするプラズマCVD処理などがあるが、いずれの方法でも単層膜から多層膜まで処理可能であり、本願発明のモリブデン耐熱合金を母材とした場合に、優れた密着性を発揮できる。   The formation method of a coating layer is not specifically limited, A film can be formed by a well-known method. Typical methods include PVD (Physical Vapor Deposition) processing such as arc ion plating and sputtering, CVD (Chemical Vapor Deposition) processing that coats by chemical reaction, and plasma CVD processing that decomposes and ionizes gaseous elements by plasma. However, any method can process from a single layer film to a multilayer film, and when the molybdenum heat-resistant alloy of the present invention is used as a base material, excellent adhesion can be exhibited.

このように、本発明のモリブデン耐熱合金はMoを主成分とする第1の相と、Ti、Zr、Hfの少なくとも1つの炭窒化物を主成分とする第2の相と、第2の相の周囲に設けられ、MoとTi、Zr、Hfの少なくとも1つの炭窒化物を含む固溶体を有する第3の相とを有し、残部が不可避不純物である。   Thus, the molybdenum heat-resistant alloy of the present invention includes a first phase mainly composed of Mo, a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf, and a second phase. And a third phase having Mo and a solid solution containing at least one carbonitride of Ti, Zr, and Hf, the balance being inevitable impurities.

そのため、本発明のモリブデン耐熱合金を用いた摩擦攪拌接合用工具は従来よりも接合対象物(加工対象物)の高融点化に対応した耐力や硬度等の物性と実用性の双方を充足する。   Therefore, the friction stir welding tool using the molybdenum heat-resistant alloy of the present invention satisfies both physical properties such as proof stress and hardness corresponding to the high melting point of the object to be joined (working object) and practicality.

以下、実施例に基づき、本発明をさらに詳細に説明する。   Hereinafter, based on an Example, this invention is demonstrated in detail.

(実施例1)
TiCN含有量の異なるモリブデン耐熱合金を用いて摩擦攪拌接合用工具を作製し、得られたモリブデン耐熱合金の特性を評価し、さらに、摩擦攪拌接合用工具の性能を評価した。具体的な手順は以下の通りである。
Example 1
Friction stir welding tools were prepared using molybdenum heat-resistant alloys having different TiCN contents, the characteristics of the obtained molybdenum heat-resistant alloys were evaluated, and the performance of the friction stir welding tools was further evaluated. The specific procedure is as follows.

<試料の作製>
まず、原料としてMo粉末、TiCN粉末を用意した。具体的には、Mo粉末は純度99.99質量%以上、Fsss法による平均粒径が4.3μmのものを用いた。
<Preparation of sample>
First, Mo powder and TiCN powder were prepared as raw materials. Specifically, Mo powder having a purity of 99.99% by mass or more and an average particle diameter by the Fsss method of 4.3 μm was used.

また、TiCN粉末には、株式会社アライドマテリアル製のTiCN粉末・品種名5OR08で、Fsss法による平均粒径が0.8μmのものを用いた。   The TiCN powder used was TiCN powder manufactured by Allied Material Co., Ltd., product type 5OR08, with an average particle diameter of 0.8 μm by the Fsss method.

成形性を促進するバインダーとしてパラフィンを用い、上記粉末全体の重量に対し2質量%を添加した。   Paraffin was used as a binder for promoting moldability, and 2% by mass was added to the weight of the whole powder.

次に、これらの粉末を後述する表1に示す配合比率で、乳鉢で混合して混合粉末を作製し、一軸式プレス機を用いて、温度20℃、成形圧3ton/cmの条件下で圧縮成形し、成形体を得た。 Next, these powders are mixed in a mortar at the blending ratio shown in Table 1 to be described later to produce a mixed powder, and using a single screw press machine, at a temperature of 20 ° C. and a molding pressure of 3 ton / cm 3 . The molded product was obtained by compression molding.

次に、得られた成形体を水素雰囲気下(大気圧)で温度1900℃で加熱し、焼結を試みた。   Next, the obtained molded body was heated at a temperature of 1900 ° C. in a hydrogen atmosphere (atmospheric pressure) to attempt sintering.

次に、焼結体を温度1600℃、Ar雰囲気下、圧力202.7MPaでHIP処理を行いモリブデン耐熱合金を作製し、切削加工および研削加工を経てFSW用工具を作製した。   Next, the sintered body was subjected to HIP treatment at a temperature of 1600 ° C. in an Ar atmosphere at a pressure of 202.7 MPa to prepare a molybdenum heat-resistant alloy, and a FSW tool was manufactured through cutting and grinding.

<相対密度測定>
次に、得られたモリブデン耐熱合金の相対密度を測定した。ここでいう相対密度とは、作製した試料(バルク)について測定した密度を理論密度で除して%で表した値である。
<Relative density measurement>
Next, the relative density of the obtained molybdenum heat-resistant alloy was measured. The relative density here is a value expressed by% by dividing the density measured for the prepared sample (bulk) by the theoretical density.

以下、具体的な測定方法について説明する。
(バルク密度の測定)
バルク密度はアルキメデス法により求めた。具体的には、空中と水中での重量を測定し、下記計算式を用いてバルク密度を求めた。
バルク密度=空中重量/(空中重量−水中重量)×水の密度
Hereinafter, a specific measurement method will be described.
(Bulk density measurement)
The bulk density was determined by the Archimedes method. Specifically, the weight in the air and water was measured, and the bulk density was determined using the following formula.
Bulk density = weight in air / (weight in air-weight in water) x density of water

(理論密度の測定)
まず、以下の手順でMo−TiCN合金の理論密度を求めた。
(Measurement of theoretical density)
First, the theoretical density of the Mo—TiCN alloy was determined by the following procedure.

(1)ICP−AESによりバルク材中のTiの質量比率(0〜1)を求め、化学分析によりC、Nの質量比率も求め、TiCNの質量比率(Zc)を算出し、Moの質量比率(Zm)を1−Zcとして算出した。 (1) The mass ratio (0 to 1) of Ti in the bulk material is obtained by ICP-AES, the mass ratio of C and N is also obtained by chemical analysis, the mass ratio (Zc) of TiCN is calculated, and the mass ratio of Mo (Zm) was calculated as 1-Zc.

(2)Moの密度をMm(=10.2g/cm)、TiCNの密度をMc(=5.1g/cm)とし、上記質量比率を体積比率に換算した。
即ち、TiCNを添加した場合のTiCNの体積比率は以下のように表される。
TiCNの体積比率=[Zc/Mc]/[Zc/Mc+Zm/Mm]
また、Moの体積比率は以下のように表される。
Moの体積比率=[Zm/Mm]/[Zc/Mc+Zm/Mm]
(2) The density of Mo was Mm (= 10.2 g / cm 3 ), the density of TiCN was Mc (= 5.1 g / cm 3 ), and the mass ratio was converted into a volume ratio.
That is, the volume ratio of TiCN when TiCN is added is expressed as follows.
TiCN volume ratio = [Zc / Mc] / [Zc / Mc + Zm / Mm]
Moreover, the volume ratio of Mo is represented as follows.
Mo volume ratio = [Zm / Mm] / [Zc / Mc + Zm / Mm]

(3)求めた体積比率に密度を乗じてバルク全体の理論密度を求めた。最後に、バルク密度を理論密度で除して相対密度を求めた。 (3) The theoretical density of the entire bulk was obtained by multiplying the obtained volume ratio by the density. Finally, the bulk density was divided by the theoretical density to obtain the relative density.

<粒径測定>
次に、得られたモリブデン耐熱合金中の粒径測定を、以下に示すような線インターセプト法により、測定した。
<Particle size measurement>
Next, the particle diameter measurement in the obtained molybdenum heat-resistant alloy was measured by the line intercept method as shown below.

具体的には、まず、測定箇所となる断面について倍率1000倍の拡大写真を撮り、この写真上において、図8に示すように、任意に直線を引き、この直線が横切る対象となる結晶粒の粒子について、この直線上を横切る個々の結晶粒の粒径を測定し総和を算出した。次に、測定した粒子の径の総和と測定粒子数より平均結晶粒径を得た。なお、測定の視野は120μm×90μmとし、50個以上の粒子を測定した。   Specifically, first, an enlarged photograph at a magnification of 1000 times is taken with respect to the cross section to be measured, and on this photograph, as shown in FIG. 8, a straight line is arbitrarily drawn, and the crystal grains to be crossed by the straight line are drawn. For the particles, the particle size of each crystal grain crossing this straight line was measured, and the total sum was calculated. Next, an average crystal grain size was obtained from the total diameter of the measured particles and the number of measured particles. The field of measurement was 120 μm × 90 μm, and 50 or more particles were measured.

また、観察された結晶粒がMo、TiCNのいずれであるかの判断はEPMAによる線分析で行った。   Further, whether the observed crystal grains were Mo or TiCN was determined by a line analysis using EPMA.

<硬度測定>
モリブデン耐熱合金の硬度測定は(株)アカシ製マイクロビッカース硬度計(型番:AVK)を用い、大気中20℃にて測定荷重20kgを加えることにより、ビッカース硬度を測定した。測定点数は5点とし、平均値を算出した。
<Hardness measurement>
The hardness of the molybdenum heat-resistant alloy was measured by using a micro Vickers hardness meter (model number: AVK) manufactured by Akashi Co., Ltd. and applying a measurement load of 20 kg at 20 ° C. in the atmosphere. The number of measurement points was 5 and the average value was calculated.

<0.2%耐力測定>
摩擦攪拌接合用工具は、回転しながら工具の横移動により接合を実施するため、高温での回転曲げに対する強度が必要であるが、高温回転曲げ試験は特殊である。そのためここでは単純曲げ試験により高温強度を評価した。さらに摩擦攪拌接合用工具は耐変形性が要求されるため、同じ歪量での評価を実施することを目的として便宜上0.2%の歪を生じた際の応力、すなわち0.2%耐力を用いた(一般に0.2%耐力は引張試験時、降伏点が不明瞭な材料の評価に使用される)。
<0.2% proof stress measurement>
Since the friction stir welding tool performs welding by lateral movement of the tool while rotating, the strength against rotational bending at high temperature is necessary, but the high temperature rotational bending test is special. Therefore, the high temperature strength was evaluated here by a simple bending test. Furthermore, since the friction stir welding tool is required to have deformation resistance, for the purpose of carrying out the evaluation with the same amount of strain, the stress when 0.2% strain is generated for convenience, that is, 0.2% proof stress. (In general, 0.2% proof stress is used for evaluation of a material whose yield point is unclear during a tensile test).

0.2%耐力は、以下の手順により測定した。
まず、モリブデン耐熱合金を長さ:約25mm、幅:2.5mm、厚さ:1.0mmとなるように加工し、表面を#600のSiC研磨紙を用いて研磨した。
The 0.2% proof stress was measured by the following procedure.
First, a molybdenum heat-resistant alloy was processed to have a length: about 25 mm, a width: 2.5 mm, and a thickness: 1.0 mm, and the surface was polished using # 600 SiC polishing paper.

次に、試料をピン間隔が16mmとなるようにインストロン社製高温万能試験機(型番:5867型)にセットし、Ar雰囲気下で、1200℃で、クロスヘッドスピード1mm/minでヘッドを試料に押し付けて3点曲げ試験を行い、0.2%耐力を測定した。0.2%耐力は、3点曲げ試験における曲げ応力と歪みを下記の式を用いて算出して応力歪み線図を描き、0.2%の永久歪みが生じる応力を解析することによって求めた。
曲げ応力=3FL/2bh
曲げ歪み=6sh/L
ここで、F:試験荷重(N)、L:支点間距離(mm)、b:試験片の幅(mm)、h:試験片の厚さ(mm)、s:たわみ量とする。
Next, the sample is set in an Instron high-temperature universal testing machine (model number: 5867 type) so that the pin interval is 16 mm, and the head is sampled at 1200 ° C. and a crosshead speed of 1 mm / min in an Ar atmosphere. A three-point bending test was performed by pressing to a 0.2% proof stress. The 0.2% proof stress was obtained by calculating the bending stress and strain in the three-point bending test using the following formula, drawing a stress-strain diagram, and analyzing the stress that causes 0.2% permanent strain. .
Bending stress = 3FL / 2bh 2
Bending strain = 6sh / L 2
Here, F: test load (N), L: distance between support points (mm), b: width of test piece (mm), h: thickness of test piece (mm), and s: deflection amount.

<FSW用工具の性能評価試験>
FSW用工具の性能評価は、以下の手順により行った。
日立製作所製2次元摩擦攪拌接合装置を用い、工具回転速度600rpm、走行速度100mm/min、工具押し込み量2.5mm、走行距離100mmとして、SUS304の突合せ接合を行い工具の摩耗量を評価した。
以上の試験条件および試験結果を表1に示す。
<Performance evaluation test of FSW tool>
The performance evaluation of the FSW tool was performed according to the following procedure.
Using a Hitachi two-dimensional friction stir welding apparatus, SUS304 was butt-joined at a tool rotation speed of 600 rpm, a running speed of 100 mm / min, a tool pushing amount of 2.5 mm, and a running distance of 100 mm, and the amount of wear of the tool was evaluated.
The above test conditions and test results are shown in Table 1.

表1から明らかなように、TiCN粉末の配合割合が5〜50質量%のもの(本発明品)は、この範囲外の比率でTiCNを配合したもの(比較例1、2)、この範囲内にある配合割合のTiCを配合したもの(比較例3、4)に比べて室温硬度と0.2%耐力が優れていた。即ち、TiCNの適正な配合比率による室温硬度と0.2%耐力の向上が確認された。ここで、TiCの配合比率を16質量%までとしているのは、16質量%を超えると焼結後の密度が低くなり、室温硬度および高温での0.2%耐力が著しく低下したため、比較例として適切でないと考えたためである。   As is apparent from Table 1, when the proportion of TiCN powder is 5 to 50% by mass (product of the present invention), TiCN is blended at a ratio outside this range (Comparative Examples 1 and 2), within this range. The room temperature hardness and the 0.2% proof stress were superior to those in which TiC was blended in a certain proportion (Comparative Examples 3 and 4). That is, it was confirmed that the room temperature hardness and the 0.2% proof stress were improved by the proper mixing ratio of TiCN. Here, the mixing ratio of TiC is set to 16% by mass. When the content exceeds 16% by mass, the density after sintering becomes low, and the room temperature hardness and the 0.2% proof stress at high temperature are remarkably lowered. This is because it was not appropriate.

また、10〜40質量%のものは、さらに室温硬度と0.2%耐力を向上できることがわかった。   Moreover, it turned out that the thing of 10-40 mass% can improve room temperature hardness and 0.2% yield strength further.

同様に、ZrCN、HfCNについても、TiCNと同等の室温硬度と0.2%耐力が得られることが確認された。   Similarly, for ZrCN and HfCN, it was confirmed that room temperature hardness and 0.2% yield strength equivalent to TiCN were obtained.

次に、これら炭窒化物を添加したモリブデン耐熱合金を素材として用い、摩擦攪拌接合用工具用工具を製作し、SUS304の線接合を行い、比較例の合金を用いて作製した摩擦攪拌接合用工具と比較を行った結果、表1に示した本発明の範囲内の合金を用いた場合には、摩擦攪拌接合用工具のピン部およびショルダー部における摩耗はほとんど認められなかった。しかし、比較例1、3、4の合金を用いた場合には、摩擦攪拌接合用工具のピン部およびショルダー部の摩耗が認められた。また、比較例2の場合には室温硬度測定時、ダイヤモンド圧子の角部からクラックが発生したため、他の例に比較し硬度は高いが靭性が低いことがわかった。また摩擦攪拌接合用工具のピン部とショルダー部の境界部においてクラックの発生が認められた。   Next, using the heat-resistant molybdenum alloy added with carbonitride as a raw material, a friction stir welding tool tool is manufactured, and SUS304 wire bonding is performed, and the friction stir welding tool manufactured using the comparative alloy is used. As a result, when the alloy within the range of the present invention shown in Table 1 was used, almost no wear was observed in the pin portion and the shoulder portion of the friction stir welding tool. However, when the alloys of Comparative Examples 1, 3, and 4 were used, wear of the pin portion and the shoulder portion of the friction stir welding tool was observed. Moreover, in the case of the comparative example 2, since the crack generate | occur | produced from the corner | angular part of the diamond indenter at the time of room temperature hardness measurement, it turned out that hardness is high compared with another example, but toughness is low. Moreover, generation | occurrence | production of the crack was recognized in the boundary part of the pin part and shoulder part of the tool for friction stir welding.

<X線回折試験>
次に、上記の範囲のうち、Mo粉末が70質量%、TiCN粉末が30質量%としたもの、Mo粉末が60質量%、TiCN粉末が40質量%としたもの、および、Mo粉末が50質量%、TiCN粉末が50質量%として合金を製造したものについて、以下の条件でX線回折を行った。具体的な条件は以下の通りである。
<X-ray diffraction test>
Next, among the above ranges, Mo powder is 70% by mass, TiCN powder is 30% by mass, Mo powder is 60% by mass, TiCN powder is 40% by mass, and Mo powder is 50% by mass. %, And an alloy produced with 50% by mass of TiCN powder was subjected to X-ray diffraction under the following conditions. Specific conditions are as follows.

装置:(株)リガク製X線回折装置(型番:RAD-IIB)
管球:Cu(KαX線回折)
発散スリット及び散乱スリットの開き角:1°
受光スリットの開き幅:0.3mm
モノクロメーター用受光スリットの開き幅:0.6mm
管電流:30mA
管電圧:40kV
スキャンスピード:1.0°/min
結果を図9に示す。
Apparatus: X-ray diffractometer manufactured by Rigaku Corporation (model number: RAD-IIB)
Tube: Cu (Kα X-ray diffraction)
Divergence slit and scattering slit opening angle: 1 °
Opening width of light receiving slit: 0.3 mm
Opening width of monochromator light receiving slit: 0.6mm
Tube current: 30 mA
Tube voltage: 40 kV
Scan speed: 1.0 ° / min
The results are shown in FIG.

図9に示すように、X線回折により得られたピークは、MoとTiCNに起因するピークのみが観察され、TiCNの質量比率が30%、40%、50%いずれの場合も、TiCNが分解することによって生成される不可避化合物に起因するピークは見受けられなかったので、TiCNの分解は生じていないことが分かる。   As shown in FIG. 9, the peak obtained by X-ray diffraction is only observed due to Mo and TiCN, and TiCN is decomposed when the mass ratio of TiCN is 30%, 40%, or 50%. As a result, no peak due to the inevitable compound produced was found, so that it was found that TiCN was not decomposed.

(実施例2)
次に、TiCN粉末の配合比率を30質量%とし、第2相中のTiCNの粒径と最大粒径、ならびにMoの平均粒径を変えた摩擦攪拌接合用工具を製作し、室温硬度と0.2%耐力の評価を行い、摩擦攪拌接合試験を行った。その試験条件と試験結果を表2に示す。
(Example 2)
Next, a friction stir welding tool in which the mixing ratio of the TiCN powder was 30% by mass, the TiCN particle size and the maximum particle size in the second phase, and the average particle size of Mo were changed was manufactured. .2% proof stress was evaluated and a friction stir welding test was conducted. The test conditions and test results are shown in Table 2.

表2から明らかなように、本発明に示すTiCN相の平均粒径を0.3μm〜10μm、最大粒径が1.4μmから30μmとしたものは、その範囲外のもの(比較例5〜8)に比べて、室温硬度と0.2%耐力が優れることがわかった。比較例5、6においては、いずれも密度が75〜93%以下の範囲でバラツキが生じ、そのため評価不能な試験体が多く認められ、信頼性に劣る結果となった。   As is apparent from Table 2, the average particle size of the TiCN phase shown in the present invention is 0.3 μm to 10 μm, and the maximum particle size is 1.4 μm to 30 μm. ), The room temperature hardness and the 0.2% proof stress were superior. In Comparative Examples 5 and 6, the density was varied in the range of 75 to 93% or less, and therefore many test specimens that could not be evaluated were recognized, resulting in poor reliability.

また、Mo相の平均粒径を0.3〜20μmとしたものは、その範囲外のものに比べて、室温硬度と0.2%耐力が優れることがわかった。比較例7、8に示すMo相の平均粒径が0.4μmおよび25μmの試験体は、比較例5、6と同様、密度バラツキが大きく評価不能であった。   Moreover, it turned out that what set the average particle diameter of Mo phase to 0.3-20 micrometers is excellent in room temperature hardness and 0.2% yield strength compared with the thing outside the range. As in Comparative Examples 5 and 6, the specimens having the average particle diameter of the Mo phase shown in Comparative Examples 7 and 8 with 0.4 μm and 25 μm had large density variations and could not be evaluated.

さらに、上記の範囲内の配合比率にてモリブデン耐熱合金を焼結して摩擦攪拌接合用工具を製作し、SUS304の線接合を行った結果、摩擦攪拌接合用工具のピン部およびショルダー部における摩耗および塑性変形はほとんど認められず、より好ましい形態であることがわかった。   Furthermore, as a result of producing a friction stir welding tool by sintering a molybdenum heat-resistant alloy at a blending ratio within the above range and performing SUS304 wire joining, wear in the pin portion and shoulder portion of the friction stir welding tool Further, almost no plastic deformation was observed, and it was found to be a more preferable form.

また、上記の効果はTiCN粉末の配合比率が30質量%の場合について述べたが、表1に記載の本発明の範囲内の組成であれば同様の効果が得られた。   Moreover, although said effect was described about the case where the mixture ratio of TiCN powder is 30 mass%, the same effect was acquired if it was a composition within the range of this invention of Table 1.

(実施例3)
次に、Mo粉末が70質量%、TiCN粉末が30質量%とし、他は実施例1と同様にて合金を製造し、合金中のTiCN粒のうち、粒径が3.0〜5.0μmのものの個数割合と合金の特性との関係についての評価を行った。試験条件および試験結果を表3に示す。なお、3.0〜5.0μmのものの個数割合は、株式会社アライドマテリアル製の炭窒化チタン粉末(品種名5MP15、5MP30)を用い、それらを分級処理して調整することにより制御した。
(Example 3)
Next, 70 mass% of Mo powder and 30 mass% of TiCN powder were used, and the other was manufactured in the same manner as in Example 1, and among the TiCN grains in the alloy, the particle diameter was 3.0 to 5.0 µm. Evaluation was made on the relationship between the number ratio of the alloy and the characteristics of the alloy. Test conditions and test results are shown in Table 3. In addition, the number ratio of 3.0-5.0 micrometers thing was controlled by classifying and adjusting them using the titanium carbonitride powder (variety name 5MP15, 5MP30) by Allied Material Co., Ltd.

表3に示すように、合金中のTiCN粒のうち、粒径が3.0〜5.0μmのものの個数割合が40%と60%のものは、30%のものと比べて室温硬度と0.2%耐力が優れていた。   As shown in Table 3, among TiCN grains in the alloy, the number ratio of particles having a particle size of 3.0 to 5.0 μm is 40% and 60%, and the room temperature hardness is 0 compared to 30%. .2% yield strength was excellent.

また、60%よりも高いものは、非常に均一な粒度の粉末であり得られ難く、実質的に粉末製造が不可能であり、評価不能であった。   Moreover, it was difficult to obtain a powder having a particle size higher than 60% because it was very difficult to obtain a powder having a very uniform particle size.

この結果から、合金中のTiCN粒のうち、3.0〜5.0μmのものの個数割合が40%〜60%のものは、室温硬度と高温での0.2%耐力に優れることがわかった。一方、比較例に記載したように、3.0〜5.0μmのものの個数割合が30%の場合には、室温硬度と高温での0.2%耐力が著しく低下するものではないが、密度が低いため強度のばらつきを生じやすくなるため好ましくないことがわかった。また、3.0〜5.0μmのものの個数割合が60%の場合には、さらに密度が低くなり製作が困難であった。   From this result, it was found that among the TiCN grains in the alloy, those having a number ratio of 3.0 to 5.0 μm having a number ratio of 40% to 60% are excellent in room temperature hardness and 0.2% proof stress at high temperature. . On the other hand, as described in the comparative example, when the number ratio of 3.0 to 5.0 μm is 30%, the room temperature hardness and the 0.2% proof stress at high temperature are not significantly reduced. It was found that the variation in strength is apt to occur because of a low value, which is not preferable. In addition, when the number ratio of 3.0 to 5.0 μm was 60%, the density was further lowered and it was difficult to produce.

さらに、上記の範囲内の配合比率にてモリブデン耐熱合金を焼結して摩擦攪拌接合用工具を製作し、SUS304の線接合を行った結果、摩擦攪拌接合用工具のピン部およびショルダー部における摩耗および塑性変形はほとんど認められず、より好ましい形態であることがわかった。   Furthermore, as a result of producing a friction stir welding tool by sintering a molybdenum heat-resistant alloy at a blending ratio within the above range and performing SUS304 wire joining, wear in the pin portion and shoulder portion of the friction stir welding tool Further, almost no plastic deformation was observed, and it was found to be a more preferable form.

また、上記の効果はTiCN粉末の配合比率が30質量%の場合について述べたが、表1に記載の本発明の範囲内の組成であれば同様の効果が得られた。   Moreover, although said effect was described about the case where the mixture ratio of TiCN powder is 30 mass%, the same effect was acquired if it was a composition within the range of this invention of Table 1.

(実施例4)
次に、Mo粉末が70質量%、TiCN粉末が30質量%とし、他は実施例1と同様にて合金を製造し、合金中のTiCN粒のうち、粒径が1.5〜3.5μmのものの個数割合、および5.0〜7.0μmのものの個数割合と合金の特性との関係についての評価を行った。試験条件および試験結果を表4に示す。なお、1.5〜3.5μmのものの個数割合、および5.0〜7.0μmのものの個数割合は、平均粒径2.0μmのTiCN粉末と5.5μmのTiCN粉末とを混合し、それら原料粉末の混合比率を変えることにより制御した。
Example 4
Next, 70 mass% of Mo powder and 30 mass% of TiCN powder were used, and the other was manufactured in the same manner as in Example 1. Among the TiCN grains in the alloy, the particle diameter was 1.5 to 3.5 μm. Evaluation was made on the relationship between the number ratio of the steel and the ratio of the number ratio of 5.0 to 7.0 μm and the characteristics of the alloy. Test conditions and test results are shown in Table 4. In addition, the number ratio of 1.5 to 3.5 μm and the number ratio of 5.0 to 7.0 μm are obtained by mixing TiCN powder with an average particle diameter of 2.0 μm and TiCN powder with 5.5 μm, It was controlled by changing the mixing ratio of the raw material powder.

表4に示すように、合金中のTiCN粒のうち、粒径が1.5〜3.5μmのものの個数割合が20%と40%のものは、15%、45%のものと比べて室温硬度、0.2%耐力、および相対密度が優れていた。   As shown in Table 4, among the TiCN grains in the alloy, the number ratio of 20% and 40% having a particle size of 1.5 to 3.5 μm is room temperature compared to 15% and 45%. Hardness, 0.2% proof stress, and relative density were excellent.

同様に、合金中のTiCN粒のうち、粒径が5.0〜7.0μmのものの個数割合が10%と30%のものは、5%、35%のものと比べて室温硬度、0.2%耐力、および相対密度が優れていた。   Similarly, among the TiCN grains in the alloy, those having a particle size of 5.0 to 7.0 μm with a number ratio of 10% and 30% have a room temperature hardness of 0.5% compared to 5% and 35%. 2% yield strength and relative density were excellent.

この結果から、合金中のTiCN粒のうち、粒径が1.5〜3.5μmのものの個数割合が20%〜40%で、かつ粒径が5.0〜7.0μmのものの個数割合が10%〜30%のものは、室温硬度、0.2%耐力、および相対密度に優れることがわかった。一方、比較例に示したように、TiCN粒の粒径が1.5〜3.5μmのものの個数割合が15%で、かつ、5.0〜7.0μmのものの個数割合が35%の場合、および1.5〜3.5μmのものの個数割合が45%で、かつ、5.0〜7.0μmのものの個数割合が5%の場合には、室温硬度と高温での0.2%耐力が著しく低下するものではないが、密度が低いため強度のばらつきを生じやすくなるため好ましくないことがわかった。   From this result, among TiCN grains in the alloy, the number ratio of particles having a particle size of 1.5 to 3.5 μm is 20% to 40% and the number ratio of particles having a particle size of 5.0 to 7.0 μm is 10% to 30% were found to be excellent in room temperature hardness, 0.2% proof stress, and relative density. On the other hand, as shown in the comparative example, the number ratio of TiCN grains having a particle size of 1.5 to 3.5 μm is 15% and the number ratio of 5.0 to 7.0 μm is 35%. , And when the number ratio of those of 1.5 to 3.5 μm is 45% and the number ratio of 5.0 to 7.0 μm is 5%, the room temperature hardness and the 0.2% yield strength at high temperature However, it was found that it is not preferable because the density is low and the strength is likely to vary.

さらに、上記の範囲内の配合比率にてモリブデン耐熱合金を焼結して摩擦攪拌接合用工具を製作し、SUS304の線接合を行った結果、摩擦攪拌接合用工具のピン部およびショルダー部における摩耗および塑性変形はほとんど認められず、より好ましい形態であることがわかった。   Furthermore, as a result of producing a friction stir welding tool by sintering a molybdenum heat-resistant alloy at a blending ratio within the above range and performing SUS304 wire joining, wear in the pin portion and shoulder portion of the friction stir welding tool Further, almost no plastic deformation was observed, and it was found to be a more preferable form.

また、上記の効果はTiCN粉末の配合比率が30質量%の場合について述べたが、表1に記載の本発明の範囲内の組成であれば同様の効果が得られた。   Moreover, although said effect was described about the case where the mixture ratio of TiCN powder is 30 mass%, the same effect was acquired if it was a composition within the range of this invention of Table 1.

(実施例5)
実施例および比較例の試料を電子顕微鏡で撮影し、組織の定量分析を行った。具体的な手順は以下の通りである。
(Example 5)
The samples of Examples and Comparative Examples were photographed with an electron microscope, and the tissues were quantitatively analyzed. The specific procedure is as follows.

<分析用試料の作製>
まず、実施例として表1に示す「本発明3」の試料を、比較例として表1に示す「比較例4」の試料を作製した。なお、作成した焼結体の寸法は直径20mm、高さ20mmである。
<Preparation of sample for analysis>
First, a sample of “Invention 3” shown in Table 1 as an example and a sample of “Comparative Example 4” shown in Table 1 as a comparative example were prepared. In addition, the dimension of the produced sintered compact is 20 mm in diameter and 20 mm in height.

次に、得られた焼結体から10mm×5mm×5mmの立方体形状の試料片を切り出し、メタクリル酸メチルを主成分とする熱間埋込樹脂に埋め込んだ。   Next, a 10 mm × 5 mm × 5 mm cubic sample piece was cut out from the obtained sintered body and embedded in a hot embedding resin mainly composed of methyl methacrylate.

次に、#180のSiCペーパーで表面を研磨し、さらに公知の研磨機にて粒径9μmのダイヤモンドスラリーで粗研磨を行った。   Next, the surface was polished with # 180 SiC paper, and further coarsely polished with a diamond slurry having a particle diameter of 9 μm using a known polishing machine.

次に、公知の研磨機にて粒径3μmのダイヤモンドスラリーで中仕上げ研磨を行い、さらに粒径3μmのダイヤモンドスラリーを吹き付けた不織布で仕上げ研磨を行った。   Next, intermediate finishing polishing was performed with a diamond slurry having a particle size of 3 μm using a known polishing machine, and further, final polishing was performed with a nonwoven fabric sprayed with a diamond slurry having a particle size of 3 μm.

最後に、島津製作所製イオンコーター(機種名:ION COATER,IC50)を用いて、イオン電流3.5mA、蒸着時間3minの条件下でAuを試料表面に蒸着させた。   Finally, Au was vapor-deposited on the sample surface using an ion coater (model name: ION COATER, IC50) manufactured by Shimadzu Corporation under the conditions of an ion current of 3.5 mA and a vapor deposition time of 3 min.

<撮影・分析条件>
試料の観察と分析は以下の条件下で行った。
まず、装置として日立製作所製走査型電子顕微鏡(FE-SEM/EDX)S−4200を用い、分析はエネルギー分散型X線分析で定量分析を行った。
<Shooting and analysis conditions>
The sample was observed and analyzed under the following conditions.
First, Hitachi Electron Scanning Electron Microscope (FE-SEM / EDX) S-4200 was used as an apparatus, and the analysis was carried out quantitatively by energy dispersive X-ray analysis.

この際、加速電圧は15kV、エミッション電流は10μAとし、撮影倍率は「本発明3」が8000倍、「比較例4」が5000倍とした。   At this time, the acceleration voltage was 15 kV, the emission current was 10 μA, and the imaging magnification was 8000 times for “Invention 3” and 5000 times for “Comparative Example 4”.

また、分析は撮影した像の濃淡から、濃色部、淡色部、および濃色部と淡色部の中間的な色の中間部の3箇所を選んでTiとMoの質量%を測定した。   In the analysis, three parts of the dark color portion, the light color portion, and the intermediate portion of the intermediate color between the dark color portion and the light color portion were selected from the density of the photographed image, and the mass% of Ti and Mo was measured.

撮影した電子顕微鏡写真を図10および図11に、分析結果を表5に示す。なお、表1における丸数字は、図10および図11において分析した場所を示すものであり、図10および図11では白い線で囲まれた四角形の領域で現されている。   The photographed electron micrographs are shown in FIGS. 10 and 11, and the analysis results are shown in Table 5. The circled numbers in Table 1 indicate the locations analyzed in FIGS. 10 and 11, and are represented by square areas surrounded by white lines in FIGS. 10 and 11.

図10および表1に示すように、比較例4の試料は、淡色部はMoが主成分であり、濃色部はTiが主成分であり、中間色部は濃色部と淡色部の中間の組成であった。
また、中間色部の面積が濃色部の面積よりも大きかった。
As shown in FIG. 10 and Table 1, in the sample of Comparative Example 4, the light color portion is mainly composed of Mo, the dark color portion is mainly composed of Ti, and the intermediate color portion is intermediate between the dark color portion and the light color portion. It was a composition.
Further, the area of the intermediate color portion was larger than the area of the dark color portion.

この結果から、淡色部は第1の相、濃色部は第2の相、中間色部が第3の相に該当することがわかった。また比較例4の試料は、第3の相が第2の相よりも成長していることが分かった。   From this result, it was found that the light color portion corresponds to the first phase, the dark color portion corresponds to the second phase, and the intermediate color portion corresponds to the third phase. In the sample of Comparative Example 4, it was found that the third phase grew more than the second phase.

一方、図11および表1に示すように、本発明3の試料も、淡色部はMoが主成分であり、濃色部はTiが主成分であり、中間色部は濃色部と淡色部の中間の組成であったが、中間色部の面積が写真からは判別するのが困難なほど小さかった。   On the other hand, as shown in FIG. 11 and Table 1, also in the sample of the present invention 3, the light color part is mainly composed of Mo, the dark color part is mainly composed of Ti, and the intermediate color part is composed of the dark color part and the light color part. Although the composition was intermediate, the area of the intermediate color portion was so small that it was difficult to distinguish from the photograph.

そのため、TiCNを用いたことにより、第3の相の成長が抑制されたことが確認できた。   Therefore, it was confirmed that the growth of the third phase was suppressed by using TiCN.

以上、本発明を実施形態および実施例に基づき説明したが、本発明は上記した実施形態に限定されることはない。   As mentioned above, although this invention was demonstrated based on embodiment and an Example, this invention is not limited to above-described embodiment.

当業者であれば、本発明の範囲内で各種変形例や改良例に想到するのは当然のことであり、これらも本発明の範囲に属するものと了解される。   It is natural for those skilled in the art to come up with various modifications and improvements within the scope of the present invention, and it is understood that these also belong to the scope of the present invention.

例えば、上記した実施形態では、モリブデン耐熱合金を摩擦攪拌接合用工具に適用した場合について説明したが、本発明は何らこれに限定されることはなく、ガラス溶融用治工具、高温工業炉用部材、熱間押出し用ダイス、継目無製管用ピアサープラグ、射出成形用ホットランナノズル、鋳造用入子金型、抵抗加熱蒸着用容器、航空機用ジェットエンジン及びロケットエンジンなどの高温環境下で用いられる耐熱性部材に適用することができる。   For example, in the above-described embodiment, the case where a molybdenum heat-resistant alloy is applied to a friction stir welding tool has been described. However, the present invention is not limited to this, and a glass melting jig, a high-temperature industrial furnace member , Hot extrusion dies, seamless pipe piercer plugs, injection molding hot runner nozzles, casting molds, resistance heating vapor deposition containers, aircraft jet engines and rocket engines, etc. It can be applied to sex members.

101 摩擦攪拌接合用工具
102 シャンク
103 ショルダー部
104 ピン部
101 Friction stir welding tool 102 Shank 103 Shoulder part 104 Pin part

Claims (17)

Moを主成分とする第1の相と、
Ti、Zr、Hfの少なくとも1つの炭窒化物を主成分とする第2の相と、
前記第2の相の周囲に設けられ、MoとTi、Zr、Hfの少なくとも1つの炭窒化物固溶体を有する第3の相と、
を有し、残部が不可避不純物であることを特徴とするモリブデン耐熱合金。
A first phase mainly composed of Mo;
A second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf;
A third phase provided around the second phase and having at least one carbonitride solid solution of Mo and Ti, Zr, Hf;
Molybdenum heat-resistant alloy characterized in that the balance is inevitable impurities.
合金中の炭窒化物の含有量が5質量%以上50質量%以下であることを特徴とする請求項1記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to claim 1, wherein the carbonitride content in the alloy is 5 mass% or more and 50 mass% or less. 合金中の炭窒化物の含有量が10質量%以上40質量%以下であることを特徴とする請求項1記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to claim 1, wherein the carbonitride content in the alloy is 10 mass% or more and 40 mass% or less. 合金中の炭窒化物の含有量が30質量%以上40質量%以下であることを特徴とする請求項1記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to claim 1, wherein the content of carbonitride in the alloy is 30% by mass or more and 40% by mass or less. 前記第2相の炭窒化物の平均粒径が、0.3μm以上10μm以下であることを特徴とする請求項1〜4のいずれか一項に記載のモリブデン耐熱合金。   5. The molybdenum heat-resistant alloy according to claim 1, wherein an average particle size of the second phase carbonitride is 0.3 μm or more and 10 μm or less. 前記第2相の炭窒化物の平均粒径が、0.3μm以上、6μm以下であることを特徴とする請求項1〜4のいずれか一項に記載のモリブデン耐熱合金。   5. The molybdenum heat-resistant alloy according to claim 1, wherein an average particle size of the second phase carbonitride is 0.3 μm or more and 6 μm or less. 前記第2相の炭窒化物粒は、粒径が3.0〜5.0μmのものが、前記第2相の炭窒化物粒全体の40−60%の個数割合であることを特徴とする請求項1〜6のいずれか一項に記載のモリブデン耐熱合金。   The second phase carbonitride grains having a particle size of 3.0 to 5.0 μm are 40-60% of the total number of the second phase carbonitride grains. The molybdenum heat-resistant alloy as described in any one of Claims 1-6. 前記第2相の炭窒化物粒は、粒径が1.5〜3.5μmの前記第2相の炭窒化物粒全体の20−40%の個数割合であり、5.0〜7.0μmの粒子が前記第2相の炭窒化物の10−30%の個数割合であることを特徴とする請求項1〜7のいずれか一項に記載のモリブデン耐熱合金。   The second phase carbonitride grains are 20 to 40% of the total number of the second phase carbonitride grains having a particle size of 1.5 to 3.5 μm, and 5.0 to 7.0 μm. 8. The molybdenum heat-resistant alloy according to claim 1, wherein the number of the particles is 10-30% of the number of the second phase carbonitrides. 9. 前記第2相の炭窒化物の最大粒径は、1μm以上30μm以下であることを特徴とする請求項1〜6のいずれか一項に記載のモリブデン耐熱合金。   7. The molybdenum heat-resistant alloy according to claim 1, wherein the maximum particle size of the second phase carbonitride is 1 μm or more and 30 μm or less. 合金中のMoの平均粒径が0.3μm以上、20μm以下であることを特徴とする請求項1〜9のいずれか一項に記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to any one of claims 1 to 9, wherein an average particle diameter of Mo in the alloy is 0.3 µm or more and 20 µm or less. 焼結または、焼結後に熱間等方静水圧を施したことを特徴とする請求項1〜10のいずれか一項に記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to any one of claims 1 to 10, wherein hot isostatic pressure is applied after sintering or sintering. 1200℃で450MPa以上の0.2%耐力および延性を有することを特徴とする請求項1〜11のいずれか一項に記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to any one of claims 1 to 11, which has a 0.2% yield strength and ductility at 1200 ° C of 450 MPa or more. 1200℃で700MPa以上の0.2%耐力および延性を有することを特徴とする請求項1〜12のいずれか一項に記載のモリブデン耐熱合金。   The molybdenum heat-resistant alloy according to any one of claims 1 to 12, which has a 0.2% proof stress and a ductility of 700 MPa or more at 1200 ° C. 請求項1〜13のいずれか一項に記載のモリブデン耐熱合金を用いたことを特徴とする摩擦攪拌接合用工具。   A friction stir welding tool using the molybdenum heat-resistant alloy according to any one of claims 1 to 13. 請求項14記載の摩擦攪拌接合用工具の表面に、周期律表IVa、Va、VIa、IIIb族元素およびC以外のIVb族元素よりなる群から選択される少なくとも1種以上の元素、またはこれら元素群から選択される少なくとも1種以上の元素の炭化物、窒化物あるいは炭窒化物を含む被膜層を有することを特徴とする摩擦攪拌接合用工具。   At least one element selected from the group consisting of periodic table IVa, Va, VIa, group IIIb elements and group IVb elements other than C, or these elements on the surface of the friction stir welding tool according to claim 14 A friction stir welding tool having a coating layer containing carbide, nitride or carbonitride of at least one element selected from the group. 請求項14または15のいずれか一項に記載の摩擦攪拌接合用工具を有することを特徴とする摩擦攪拌装置。   A friction stirrer comprising the friction stir welding tool according to any one of claims 14 and 15. Mo粉末と、炭窒化物粉末を混合する混合工程と、
前記混合工程により得られた混合粉を室温中で圧縮成形する成形工程と、
前記成形工程により得られた成形体を少なくとも水素と窒素を含む雰囲気にて1600℃以上、2000℃以下で加熱する焼結工程と、
前記焼結工程により得られた焼結体を不活性雰囲気にて熱間等方圧加圧する加圧工程と、
を具える、請求項1〜13のいずれか一項に記載のモリブデン耐熱合金を製造する製造方法。
A mixing step of mixing Mo powder and carbonitride powder;
A molding step of compression-molding the mixed powder obtained by the mixing step at room temperature;
A sintering step of heating the molded body obtained by the molding step at 1600 ° C. or more and 2000 ° C. or less in an atmosphere containing at least hydrogen and nitrogen;
A pressurizing step of hot isostatically pressing the sintered body obtained by the sintering step in an inert atmosphere;
The manufacturing method which manufactures the molybdenum heat-resistant alloy as described in any one of Claims 1-13 provided with these.
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