JP2019073786A - Hard sintered body and rotary tool using the same - Google Patents

Hard sintered body and rotary tool using the same Download PDF

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JP2019073786A
JP2019073786A JP2017202722A JP2017202722A JP2019073786A JP 2019073786 A JP2019073786 A JP 2019073786A JP 2017202722 A JP2017202722 A JP 2017202722A JP 2017202722 A JP2017202722 A JP 2017202722A JP 2019073786 A JP2019073786 A JP 2019073786A
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phase
sintered body
sample
metal bonding
rotary tool
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大智 渡邉
Hirotomo Watanabe
大智 渡邉
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Riido KK
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Riido KK
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Priority to PCT/JP2018/038101 priority patent/WO2019078109A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/12—Non-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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide

Abstract

To provide a hard sintered body capable of being suitably used for a processing tool of a processed material consisting of metal materials which need to be processed at higher temperature, and capable of securing needed mechanical properties or durability not only under a room temperature (ordinary temperature) condition, but also under severe conditions in which the processed material is processed with heating at a high temperature, and a manufacturing method therefor.SOLUTION: In a sintered body having a hard phase constituted single or a plurality of carbide or carbonitride containing WC, and a metal bond phase consisting of transition metals and an intermetallic compound containing the transition metals, the metal bond phase is constituted with a volume ratio of 15% to 55% based on whole sintered body, Ni and Al are contained as essential components, and a L1phase (γ' phase), which is the intermetallic compound thereof, of 40 vol.% or more and a B2 phase (β phase) of 10 vol.% or less.SELECTED DRAWING: Figure 7

Description

本発明は、特に、金属材料から成る被加工材が高温に加熱されながら加工されるような過酷な条件下においても、優れた耐久性を確保することが可能な硬質焼結体及びその焼結体を用いた回転工具に関する。   The present invention provides a hard sintered body capable of securing excellent durability even under severe conditions in which a workpiece made of a metal material is processed while being heated to a high temperature, and a sintered body thereof The present invention relates to a rotary tool using a body.

近年、工具として高い耐熱性が要求される用途が飛躍的に増えている。その代表的な例として、超合金の切削・旋削加工や摩擦攪拌接合（Ｆｒｉｃｔｉｏｎ Ｓｔｉｒ Ｗｅｌｄｉｎｇ）がある。特に摩擦攪拌接合は、アルミニウム合金からなる自動車の車体フレームや鉄道車両の構体の製造方法として広く普及しているが、最も広く利用されている炭素鋼やステンレス鋼等の鉄鋼材料や耐熱性に優れた超合金への普及は未だ進んでいない。   In recent years, applications requiring high heat resistance as a tool have dramatically increased. As typical examples, there are cutting / turning processing and friction stir welding of superalloys. In particular, friction stir welding is widely used as a method of manufacturing automobile body frames made of aluminum alloy and automobile body structures of railway vehicles, but it is excellent in steel materials such as carbon steel and stainless steel, which are most widely used, and heat resistance. Dissemination to superalloys has not progressed yet.

その理由として、第一に、鉄鋼材料は、アルミニウム合金と比較して融点が高いため、軟化させるためにより大きな摩擦熱を必要とすることが挙げられる。特にステンレス鋼や超合金の場合は、ＣｒやＮｉ等の添加元素によって高温下での変形抵抗が大きくなるため、軟化させるために９００℃〜１０００℃に至る非常に大きな摩擦熱を必要とする。これは、アルミニウム合金の摩擦攪拌接合の適正温度とされる５００〜６００℃よりもはるかに高い。また、第二に、鉄鋼材料や超合金はアルミニウム合金と比較して硬いため、工具の摩耗がより発生し易いことが挙げられる。熱処理によって硬度が高められた調質鋼や、圧延によって加工硬化したステンレス鋼では、ロックウェル硬度でＨＲＣ４０（ビッカース硬度ＨＶ３９０相当）を超える硬度を有する。   The reason is that, first, since the steel material has a high melting point as compared with the aluminum alloy, it requires a larger frictional heat to be softened. In particular, in the case of stainless steels and superalloys, the deformation resistance at high temperatures is increased by the addition elements such as Cr and Ni, so very large frictional heats up to 900 ° C. to 1000 ° C. are required to soften. This is much higher than 500-600 ° C., which is considered to be the proper temperature for friction stir welding of aluminum alloys. Secondly, since steel materials and superalloys are harder than aluminum alloys, tool wear is more likely to occur. A tempered steel whose hardness has been increased by heat treatment or a stainless steel which has been work hardened by rolling has a Rockwell hardness which exceeds HRC40 (equivalent to Vickers hardness HV390).

これらの技術課題を解決するために、非常に多くの試みがなされてきた。現在、最も耐熱性に優れた工具の一つとして、特許文献１で示されたＰＣＢＮ（多結晶立方晶窒化ホウ素）を含有した焼結材料が公知である。しかしながら、この材料はカケやチッピングが発生しやすいことから普及には至っていない。
また、特許文献２で示されたＷ基合金からなる材料が公知である。特に、Ｗ−２５％ＲｅはＷ基合金の中でも常温から高温に至るまでの機械特性のバランスが良いことから普及が期待されてきた。しかしながら、硬度が不足していることから耐磨耗性に課題があるとされており普及には至っていない。 Numerous attempts have been made to solve these technical problems. At present, a sintered material containing PCBN (polycrystalline cubic boron nitride) shown in Patent Document 1 is known as one of the most heat resistant tools. However, this material has not been widely used because it is easy to cause chipping and chipping.
Further, a material made of a W-based alloy shown in Patent Document 2 is known. In particular, W-25% Re has been expected to be popular because it has a good balance of mechanical properties from normal temperature to high temperature among W-based alloys. However, since the hardness is insufficient, it is considered that there is a problem in the wear resistance and it has not been widely used.

また、特許文献３で示されたＩｒ基合金からなる材料が公知である。Ｉｒ合金は、１４００℃に至るまでほとんど硬さが変化しない非常に優れた超高温材料とされ、ＭｏやＰｔ等の高融点材料を加工するための工具としての役割も期待されている。しかしながら、常温下での硬さはビッカース硬さとしてＨＶ５００程度であり、特にプローブ挿入時の耐摩耗性に関して不安がある。   Further, a material made of an Ir-based alloy shown in Patent Document 3 is known. The Ir alloy is considered to be a very excellent ultra-high temperature material whose hardness hardly changes up to 1400 ° C., and a role as a tool for processing high melting point materials such as Mo and Pt is also expected. However, the hardness at normal temperature is about HV500 as Vickers hardness, and there is concern about wear resistance particularly when the probe is inserted.

また、Ｌ１２相（γ’相）を形成して高温特性を改善した材料として、Ｃｏ基合金からなる特許文献４，５や、Ｎｉ基合金からなる特許文献６，７，８が公知である。しかしながら、常温下での硬さはビッカース硬さとしてＨＶ５００程度であり、特にプローブ挿入時の耐摩耗性に関して不安がある。常温硬さを改善するための方法として、ＴｉＣやＴｉＢ２を添加した材料が特許文献９，１０で示されているが、硬さは向上するものの非常に脆いことから、現時点では未だ実用段階には至っていない。 In addition, Patent Documents 4 and 5 made of a Co-based alloy, and Patent Documents 6, 7 and 8 made of a Ni-based alloy are known as materials having improved L 1 2 phase (γ ′ phase) to improve high temperature characteristics. . However, the hardness at normal temperature is about HV500 as Vickers hardness, and there is concern about wear resistance particularly when the probe is inserted. Although the materials to which TiC or TiB 2 is added are shown in Patent Documents 9 and 10 as a method for improving the normal temperature hardness, since the hardness is improved but extremely brittle, it is still in the practical stage at present. Has not been reached.

添加物として耐熱性の高いモリブデンの金属間化合物を含有させる方法も公知である。特許文献１１，１２，１３では、Ｍｏ５ＳｉＢ２を含有させることにより、高温における機械特性を改善する方法が示されている。しかしながら、室温領域での靭性に乏しいとされ現時点ではほとんど普及していない。 Also known is a method of incorporating a highly heat-resistant intermetallic compound of molybdenum as an additive. Patent documents 11, 12 and 13 show a method of improving mechanical properties at high temperature by containing Mo 5 SiB 2 . However, the toughness in the room temperature region is considered to be poor and is hardly widespread at present.

最も普及が期待されているのは、常温硬さと靭性とを兼ね備えた材料として広く利用されているＷＣ−（Ｃｏ，Ｎｉ）基合金と耐熱性と靭性に優れたセラミックスである窒化珪素及びサイアロンである。   The most widely expected are WC- (Co, Ni) -based alloys widely used as a material having both normal temperature hardness and toughness and silicon nitride and sialon which are ceramics excellent in heat resistance and toughness. is there.

ＷＣ−（Ｃｏ，Ｎｉ）基合金については、例えば、特許文献１４，１５，１６において様々な添加材や添加量の検討が試みられている。しかしながら、ＷＣを結合するＣｏやＮｉ等の金属結合相の存在により、８００〜１０００℃の温度では硬度の低下やクリープ耐性の低下が著しく、変形や異常摩耗が生じるため、本格的な普及には至っていない。異常摩耗の対策として、表面に硬質層を被覆することによって改善を試みた例が特許文献１７，１８に示されているが、一方でクリープ耐性は改善されない。   For WC- (Co, Ni) -based alloys, for example, examination of various additives and addition amounts is attempted in Patent Documents 14, 15, and 16. However, due to the presence of a metal bonding phase such as Co or Ni that bonds WC, hardness and creep resistance significantly decrease at a temperature of 800 to 1000 ° C., causing deformation and abnormal wear. It has not been reached. Although the example which tried improvement by coat | covering a hard layer on the surface as a countermeasure of abnormal wear is shown by patent documents 17 and 18, creep resistance is not improved on the other hand.

また、窒化珪素及びサイアロンは、例えば特許文献１９，２０において公知であり、前述の各種技術課題を解決し得る材料として、現状最も普及が期待されているものの、突発的に工具が破砕することがあり本格的な普及には至っていない。   In addition, silicon nitride and sialon are known, for example, in Patent Documents 19 and 20, and although materials are most widely expected at present as materials capable of solving the various technical problems described above, the tool may be broken suddenly It has not reached the full-scale spread.

特表２００３−５３２５４３号公報Japanese Patent Publication No. 2003-532543 特開２００４−３５８５５６号公報JP 2004-358556 A 特開２００６−３２０９５８号公報JP, 2006-320958, A 国際公開第２００７／０３２２９３号パンフレットWO 2007/032293 pamphlet 特開２０１３−１２１６２１号公報JP, 2013-121621, A 特開２００９−２５５１７０号方向JP 2009-255170 direction 特開２０１４−０１４８２２号公報JP, 2014-014822, A 特開２０１４−１７３１６３号公報JP, 2014-173163, A 再表２０１３／０５８３３８号公報Revised 2013/058338 特開２０１４−１６９４７１号公報JP, 2014-169471, A 特開２００８−１１４２５８号公報JP, 2008-114258, A 特開２０１４−０１２８８３号公報JP, 2014-012883, A 国際公開第２０１４／１１２１５１号パンフレットInternational Publication No. 2014/112151 brochure 特開２００５−１９９２８１号公報JP 2005-199281 A 特開２００９−２１４１７０号公報JP, 2009-214170, A 特開２０１０−２６００６５号公報JP, 2010-260065, A 特表２０１１−５０４８０８号公報Japanese Patent Application Publication No. 2011-504808 特開２０１２−１３９６９４号公報Unexamined-Japanese-Patent No. 2012-139694 特開２０１１−０９８８４２号公報JP, 2011-098842, A 国際公開第２０１６／０４７３７６号パンフレットWO 2016/047376 pamphlet

本発明は、前述のような事情に鑑みてなされたものであり、その技術的課題は、炭素鋼やステンレス鋼等の鉄鋼材料や耐熱性に優れた超合金等、より高温での加工が必要な金属材料から成る被加工材の加工用工具に好適に用いることができ、室温（常温）条件下のみならず、被加工材が高温に加熱されながら加工されるような過酷な条件下においても、必要な機械特性や耐久性を確保することが可能な硬質焼結体、及びその焼結体を用いた回転工具を提供することにある。   The present invention has been made in view of the above-mentioned circumstances, and the technical problem is that steel materials such as carbon steel and stainless steel, superalloys excellent in heat resistance, etc. require processing at higher temperatures. It can be suitably used as a processing tool for workpieces made of various metallic materials, and not only under room temperature (normal temperature) conditions, but also under severe conditions where the workpiece is processed while being heated to a high temperature An object of the present invention is to provide a hard sintered body capable of securing necessary mechanical properties and durability, and a rotary tool using the sintered body.

前述の技術的課題を解決するため、本発明者は、炭化タングステンＷＣを含む単一或いは複数の炭化物及び／又は炭窒化物で構成される硬質相と、金属結合相とが粉末冶金法によって結合された焼結体において、高温特性に大きな影響を与える金属結合相の組織に着目し、常温及び高温下での機械特性や耐久性の向上を目指して開発を進めてきた。その結果、金属結合相の組織が所定の条件を満たすときに、前述の技術的課題に対して極めて優れた硬質焼結体及び回転工具が得られることを見出し、本発明に至った。   In order to solve the above-mentioned technical problems, the present inventor has connected a hard phase composed of one or more carbides and / or carbonitrides including tungsten carbide WC and a metal bonding phase by powder metallurgy. In the sintered body, focusing on the structure of the metal binder phase that greatly affects the high temperature characteristics, development has been carried out aiming to improve the mechanical characteristics and durability under normal temperature and high temperature. As a result, it has been found that when the structure of the metal bonding phase satisfies a predetermined condition, it is possible to obtain a hard sintered body and a rotary tool extremely excellent for the above-mentioned technical problems, and the present invention has been achieved.

本発明は、ＷＣを含む単一或いは複数の炭化物及び／又は炭窒化物で構成される硬質相と、遷移金属及び遷移金属を含む金属間化合物から成る金属結合相とを有する硬質焼結体であって、前記金属結合相は、Ｎｉ及びＡｌを含み、前記焼結体全体に対して１５％以上かつ５５％以下の体積比を有し、更に、該金属結合相は、該金属結合相全体に対して４０％以上の体積比のＬ１２相（γ’相）と、１０％以下の体積比のＢ２相（β相）とで構成されていることを特徴としている。 The present invention is a hard sintered body having a hard phase composed of one or more carbides and / or carbonitrides containing WC and a metal bonding phase composed of a transition metal and an intermetallic compound containing the transition metal. And the metal bonding phase contains Ni and Al, and has a volume ratio of 15% or more and 55% or less with respect to the whole sintered body, and the metal bonding phase is the entire metal bonding phase. On the other hand, it is characterized in that it is composed of L1 2 phase (γ ′ phase) having a volume ratio of 40% or more and B2 phase (β phase) having a volume ratio of 10% or less.

前記硬質焼結体において、好ましくは、前記硬質相に、ＴｉＣ，ＴｉＮ，Ｔｉ（Ｃ，Ｎ），Ｃｒ３Ｃ２，ＴａＣ，及びこれらとＷＣとの固溶体のうち何れか１つ或いは２つ以上を含んでいる。 In the hard sintered body, preferably, at least one of TiC, TiN, Ti (C, N), Cr 3 C 2, TaC, and a solid solution of these with WC in the hard phase is used. Contains.

なお、前記硬質焼結体は、金属材料から成る被加工材の形態を回転しながら変化させるための回転工具として好適である。   The hard sintered body is suitable as a rotating tool for rotating and changing the form of a workpiece made of a metal material.

前記回転工具の表面には、酸化開始温度９００℃以上の耐酸化性被覆が施されることがより好適である。   It is more preferable that an oxidation resistant coating having an oxidation start temperature of 900 ° C. or more be provided on the surface of the rotary tool.

前記回転工具の一例として、摩擦攪拌工程に用いられる回転工具が挙げられる。   As an example of the said rotary tool, the rotary tool used for a friction stirring process is mentioned.

本発明によれば、より高温での加工が必要な金属材料から成る被加工材の加工用工具に好適に用いることができ、室温条件下のみならず、被加工材が高温に加熱されながら加工されるような過酷な条件下においても、必要な機械特性や耐久性を確保することが可能な硬質焼結体、及びその焼結体を用いた回転工具を提供することができる。   According to the present invention, it can be suitably used as a processing tool for a workpiece made of a metal material that requires processing at a higher temperature, and not only at room temperature but also while processing the workpiece being heated to a high temperature It is possible to provide a hard sintered body capable of securing necessary mechanical properties and durability even under such severe conditions, and a rotary tool using the sintered body.

摩擦攪拌工程により２つの被加工材を接合する方法を示す概念図である。It is a conceptual diagram which shows the method of joining two workpieces by a friction stirring process. 走査型電子顕微鏡によって観察された試料Ｎｏ．Ｄ−１の反射電子像である。Sample No. 1 observed by a scanning electron microscope. It is a reflected electron image of D-1. 試料Ｎｏ．Ｄ−２及び試料Ｎｏ．Ｃ−４のＸ線回折プロファイルである。Sample No. D-2 and sample nos. It is a X-ray-diffraction profile of C-4. 「条件２」によって加工した後の被加工材表面の外観を示す写真である。It is a photograph which shows the external appearance of the to-be-processed material surface after processed by "condition 2". 「条件２」によって加工した後の被加工材表面の接合状態を示す写真である（欠陥なし）。It is a photograph which shows the joining state of the workpiece surface after processed by "condition 2" (there is no defect). 「条件２」によって加工した後の被加工材表面の接合状態を示す写真である（欠陥あり）。It is a photograph which shows the joining state of the workpiece surface after processed by "condition 2" (with a defect). 「条件２」によって試験を実施した試料Ｎｏ．Ｄ−２の断面形状を示す図である。Sample No. 2 for which the test was performed according to “condition 2”. It is a figure which shows the cross-sectional shape of D-2. 「条件２」によって試験を実施した試料Ｎｏ．Ｎ−４（窒化珪素（Ｓｉ３Ｎ４））の断面形状を示す図である。Sample No. 2 for which the test was performed according to “condition 2”. Is a diagram showing a sectional configuration of the N-4 (silicon nitride (Si 3 N 4)). ショルダに変形が生じた回転工具先端部の外観を示す写真である。It is a photograph which shows the external appearance of the rotary tool tip part which the deformation | transformation produced in the shoulder. 「条件１」によって試験を実施した試料Ｎｏ．Ｎ−３（Ｎｉ−Ｉｒ超合金）の工具先端部の外観を示す写真である。Sample No. 1 for which the test was performed under “condition 1”. It is a photograph which shows the external appearance of the tool tip part of N-3 (Ni-Ir super alloy). 試料Ｎｏ．Ｄ−３と試料Ｎｏ．Ｄ’−３の高温硬さの変化を示すグラフである。Sample No. D-3 and sample no. It is a graph which shows the change of the high temperature hardness of D'-3. 焼結体に発生した変色部のＸ線回折プロファイルである。It is a X-ray-diffraction profile of the discolored part which generate | occur | produced in the sintered compact. 「条件２」によって試験を実施した試料Ｎｏ．Ｄ−２の工具先端部の外観を示す写真である。Sample No. 2 for which the test was performed according to “condition 2”. It is a photograph which shows the external appearance of the tool tip part of D-2. 「条件２」によって試験を実施した試料Ｎｏ．Ｄ−１０の工具先端部の外観である。Sample No. 2 for which the test was performed according to “condition 2”. It is an external appearance of the tool tip part of D-10.

本発明に係る硬質焼結体及びそれを用いた回転工具の実施形態及び実施例について、以下に詳細に説明する。但し、本発明は、以下の実施形態や実施例の範囲に限定して解釈されるものではない。   Embodiments and examples of the hard sintered body and the rotary tool using the same according to the present invention will be described in detail below. However, the present invention is not construed as being limited to the scope of the following embodiments and examples.

前記実施形態としての硬質焼結体は、９００℃〜１０００℃に至る非常に高温条件下での加工が必要な金属材料から成る被加工材の加工用工具に好適に用いることができるもので、炭化タングステン（ＷＣ）を含む単一或いは複数の炭化物及び／又は炭窒化物で構成される硬質相と、遷移金属及び遷移金属を含む金属間化合物からなる金属結合相とが粉末冶金法によって結合されたものである。このとき、前記金属結合相は、Ｎｉ及びＡｌを含み、前記焼結体全体に対して１５体積％以上かつ５５体積％以下の体積比を有している。また、前記硬質相は、焼結体全体において前記金属結合相の体積を除いた残余を成している。   The hard sintered body according to the embodiment can be suitably used as a processing tool for a workpiece made of a metal material which requires processing under very high temperature conditions up to 900 ° C. to 1000 ° C., A hard phase composed of one or more carbides and / or carbonitrides including tungsten carbide (WC) and a metal bonding phase composed of transition metals and intermetallic compounds including transition metals are combined by powder metallurgy It is At this time, the metal bonding phase contains Ni and Al, and has a volume ratio of 15% by volume or more and 55% by volume or less with respect to the entire sintered body. Further, the hard phase constitutes the remainder excluding the volume of the metal bonding phase in the entire sintered body.

次に、図１に基づいて、本発明の焼結体によって形成された回転工具の一実施形態について説明する。なお、本実施形態では、前記焼結体を摩擦攪拌工程に用いられる回転工具に適用した場合について説明するが、例えば、Ｎｉ基超合金等の加工に代表されるような、工具を１００００ｒｐｍを超える高速で回転させることにより材料を軟化させながら切削加工や研削加工等を行うための回転工具に対しても、同様に適用することが可能である。   Next, based on FIG. 1, one Embodiment of the rotary tool formed with the sintered compact of this invention is described. In the present embodiment, although the case where the sintered body is applied to a rotary tool used in a friction stirring process is described, for example, a tool represented by processing of a Ni-based super alloy or the like exceeds 10000 rpm. The present invention can be similarly applied to a rotating tool for performing cutting, grinding, etc. while softening the material by rotating at high speed.

摩擦攪拌工程とは、回転工具を被加工材に挿入することによって摩擦熱を発生させる工程であり、この工程によって、２個の物品を互いに接合したり、被加工材の表面を改質したりすることが可能となる。図１は、２個の物品１Ａ，１Ｂを互いに接合（摩擦攪拌接合）するための実施形態の例である。   The friction stirring step is a step of generating frictional heat by inserting a rotary tool into a workpiece, and by this step, two articles are joined to each other, or the surface of the workpiece is reformed. It is possible to FIG. 1 is an example of an embodiment for bonding two articles 1A and 1B to each other (a friction stir welding).

回転工具３は、円柱状のショルダ５における略平坦な端面の中央から、該ショルダ５よりも小径のプローブ４を一体に突設することにより形成される。前記ショルダ５の端面からのプローブ４の高さは、互いに接合する被加工材１Ａ，１Ｂの厚みよりも小さく形成される。なお、被加工材の表面改質を行う場合や熱特性の大きく異なる異種材料間（例えば、金属と樹脂）で重ね接合を行う場合等、場合に応じて、該プローブ４が省略されて前記ショルダ５のみから成る円柱状の回転工具としても良い。   The rotary tool 3 is formed by integrally projecting a probe 4 having a diameter smaller than that of the shoulder 5 from the center of the substantially flat end face of the cylindrical shoulder 5. The height of the probe 4 from the end face of the shoulder 5 is smaller than the thickness of the workpieces 1A and 1B to be joined to each other. The probe 4 may be omitted depending on the case, for example, in the case of surface modification of the workpiece or in the case of overlapping bonding between dissimilar materials (for example, metal and resin) having greatly different thermal characteristics. It may be a cylindrical rotary tool consisting of only five.

次に、この回転工具３を用いて、上記被加工材１Ａ，１Ｂにおける互いに対向する端面同士を摩擦攪拌接合する方法について説明する。まず、図１に示すように、該被加工材１Ａ，１Ｂの両端面が当接させられた接合領域２の一端に、前記回転工具３を、ショルダ５が該被加工材１Ａ，１Ｂの表面に接触するがプローブ４がバックプレート６に接触しない深さまで、モータ等で回転させながらゆっくりと挿入する。すると、回転工具３と被加工材１Ａ，１Ｂとの接触部で摩擦熱が発生し、その摩擦熱によって被加工材１Ａ，１Ｂが軟化する。そして、その軟化と共に、被加工材１Ａ，１Ｂは摩擦力によって塑性変形を起こして攪拌され、その結果、被加工材１Ａ，１Ｂは回転工具３との接触部で互いに接合される。続いて、その回転工具３を接合領域２の他端方向である進行方向８に向けて移動させていくと、進行方向８に沿って連続的に接合が進み、最終的に接合領域２全体が接合される。   Next, a method of friction stir welding the end surfaces of the workpieces 1A and 1B facing each other using the rotary tool 3 will be described. First, as shown in FIG. 1, the rotary tool 3 is mounted on one end of the joint area 2 in which both end surfaces of the workpieces 1A and 1B are abutted, and the shoulder 5 is the surface of the workpieces 1A and 1B. To a depth at which the probe 4 does not contact the back plate 6, and while inserting a rotation by a motor or the like, it is inserted slowly. Then, frictional heat is generated at the contact portion between the rotary tool 3 and the workpieces 1A and 1B, and the frictional heat softens the workpieces 1A and 1B. Then, along with the softening, the workpieces 1A and 1B are plastically deformed and agitated by the frictional force, and as a result, the workpieces 1A and 1B are joined to each other at the contact portion with the rotary tool 3. Subsequently, when the rotary tool 3 is moved toward the advancing direction 8 which is the other end direction of the joining area 2, the joining advances continuously along the advancing direction 8, and finally the entire joining area 2 It is joined.

このように、摩擦攪拌工程による接合（すなわち、摩擦攪拌接合）は、被加工材１Ａ，１Ｂの部分的な溶融を伴う従来の溶接工程と異なり融点以下で処理される固相接合である。そのため、被加工材の歪みの発生を抑えることができると共に、粗大な結晶粒の発生がなく強度や耐食性に優れるという利点を有する。   Thus, the bonding by the friction stir process (that is, friction stir welding) is a solid phase bond which is processed at a melting point or lower unlike the conventional welding process involving partial melting of the workpieces 1A and 1B. Therefore, while being able to suppress generation | occurrence | production of distortion of a to-be-processed material, it has an advantage that generation | occurrence | production of a coarse crystal grain does not occur and it is excellent in intensity | strength and corrosion resistance.

次に、本発明に係る硬質焼結体及びそれによって形成された回転工具の実施例について説明する。   Next, examples of the hard sintered body and the rotary tool formed thereby according to the present invention will be described.

まず、硬質焼結体を製造する方法について説明する。   First, a method of manufacturing a hard sintered body will be described.

前記硬質相を形成する原料粉末としては、ＷＣ（ＦＳＳＳ：１．０μｍ、９９．８重量％）、ＴｉＣ（ＦＳＳＳ：１．９μｍ、９９．０重量％）、ＴｉＣＮ（ＦＳＳＳ：１．４μｍ、ＴｉＣ／ＴｉＮ＝７／３、９８．９重量％）、ＴａＣ（ＦＳＳＳ：０．９μｍ、９９．６重量％）、Ｍｏ２Ｃ（ＦＳＳＳ：１．８μｍ、９９．５重量％）、Ｃｒ３Ｃ２（ＦＳＳＳ：１．６μｍ、９９．７重量％）であり、何れも単一材料として市販されている微粉末を用いている。 As raw material powders for forming the hard phase, WC (FSSS: 1.0 μm, 99.8 wt%), TiC (FSSS: 1.9 μm, 99.0 wt%), TiCN (FSSS: 1.4 μm, TiC) / TiN = 7/3, 98.9% by weight), TaC (FSSS: 0.9 μm, 99.6% by weight), Mo 2 C (FSSS: 1.8 μm, 99.5% by weight), Cr 3 C 2 (FSSS: 1.6 μm, 99.7% by weight), and all use a fine powder commercially available as a single material.

また、前記金属結合相を形成する原料粉末としては、Ｎｉ（ＦＳＳＳ：４．３μｍ、９９．８重量％）、Ａｌ（Ｄ５０：１１μｍ、９９．８重量％）、Ｂ（ＦＳＳＳ：０．７μｍ、９５．１重量％）、Ｃｏ（ＦＳＳＳ：１．５μｍ、９９．９重量％）、Ｓｉ（Ｄ５０：２．５μｍ、９８重量％），Ｃ（Ｄ５０：３．５μｍ、９９．９重量％），Ｔｉ（Ｄ５０：１３μｍ、９９．６重量％），Ｎｂ（３２５ｍｅｓｈ、９９．５重量％），Ｔａ（３２５ｍｅｓｈ、９９．５重量％），Ｃｒ（５００ｍｅｓｈ、９９．９重量％），Ｍｏ（ＦＳＳＳ：１．６μｍ、９９．９９重量％），Ｗ（ＦＳＳＳ：０．９μｍ、９９．９重量％）であり、何れも単一材料として市販されている微粉末を用いている。   Moreover, as a raw material powder which forms the said metal-binding phase, Ni (FSSS: 4.3 micrometers, 99.8 weight%), Al (D50: 11 micrometers, 99.8 weight%), B (FSSS: 0.7 micrometers, 95.1% by weight), Co (FSSS: 1.5 μm, 99.9% by weight), Si (D50: 2.5 μm, 98% by weight), C (D50: 3.5 μm, 99.9% by weight), Ti (D 50: 13 μm, 99.6% by weight), Nb (325 mesh, 99.5% by weight), Ta (325 mesh, 99.5% by weight), Cr (500 mesh, 99.9% by weight), Mo (FSSS: The fine powder is 1.6 μm, 99.99% by weight), W (FSSS: 0.9 μm, 99.9% by weight), and all of them use a fine powder commercially available as a single material.

以上の原料粉末を所望の組成となるように秤量する。次に、ＰＰ製容器にアルコールと共に封入し、超硬球を用いたボールミルによって２４時間混合する。次に、混合粉を別容器に取り出し乾燥させ、凝集部を乳鉢を用いて再粉砕する。次に、混合粉をカーボン製の型に詰めて予備加圧を加えて圧粉成形を行う。次に、少なくとも１０Ｐａ未満の真空雰囲気中で最高到達温度が１１００〜１４００℃の範囲から選択された条件で、５０〜７０ＭＰａの加圧条件にて焼成することにより、本実施例に係る硬質焼結体が得られる。なお、焼成時の加圧は、焼結体の密度の向上を容易にするだけでなく、金属結合相に必要なＬ１２相（γ’相）の安定した生成を助長するため、無加圧焼成よりも好ましい。このとき、金属結合相におけるＬ１２相（γ’相）の割合は、該金属結合相におけるＡｌの割合の増減により調節することができる。また、前記最高到達温度が１１００℃よりも低いと、このＬ１２相（γ’相）の形成に至らず、後述するＢ２相（β相）の割合が増えてしまうため望ましくなく、その一方で、１４００℃よりも高いと、原料が溶融してしまう虞があるため望ましくない。 The above raw material powders are weighed to obtain a desired composition. Next, the container is sealed with alcohol in a PP container and mixed for 24 hours by a ball mill using cemented carbide balls. Next, the mixed powder is taken out in a separate container and dried, and the coagulated part is reground using a mortar. Next, the mixed powder is packed in a carbon mold and pre-pressurized to perform compacting. Next, the hard sintering according to the present embodiment is performed by firing under a pressure condition of 50 to 70 MPa under a condition where the highest achieved temperature is selected from the range of 1100 to 1400 ° C. in a vacuum atmosphere of at least 10 Pa. Get the body. In addition, pressurization at the time of firing not only facilitates the improvement of the density of the sintered body but also promotes the stable formation of the L1 2 phase (γ ′ phase) required for the metal bonding phase. It is preferable to baking. At this time, the ratio of the L1 2 phase (γ ′ phase) in the metal bonding phase can be adjusted by increasing or decreasing the ratio of Al in the metal bonding phase. On the other hand, if the maximum temperature reached is lower than 1100 ° C., this does not lead to the formation of the L1 2 phase (γ ′ phase), and the proportion of the B 2 phase (β phase) to be described later increases, which is not desirable. If the temperature is higher than 1400 ° C., the raw material may be melted, which is not desirable.

本実施例において試験に供した焼結体の組成一覧を表１に示す。ここで、試料Ｎｏ．Ｄ−１〜１２は本発明の実施例を示しており、試料Ｎｏ．Ｃ−１〜４はその比較例を示している。また、試料Ｎｏ．Ｄ’−２は前記試料Ｎｏ．Ｄ−２の派生例、試料Ｎｏ．Ｄ’−３は前記試料Ｎｏ．Ｄ−３の派生例をそれぞれ示しており、何れも本発明の実施例に含まれる。更に、従来例として、内製のＷＣ−Ｃｏ合金、並びに、市販のＶＣ−５０（ＣＩＳ分類）合金、Ｎｉ−Ｉｒ超合金及び窒化珪素（Ｓｉ３Ｎ４）を、試料Ｎｏ．Ｎ−１〜４にそれぞれ示している。ここで、硬質相の組成は、質量％として合計１００となるように表記されている。また、金属結合相の組成は、原子％として合計１００となるように表記されている。その上で、焼結体全体に対する金属結合相の割合を、体積％として表記している。なお、本実施例の全ての材料は、組成の混合則によって導出される理論密度に対して、アルキメデス法を用いて評価した結果が少なくとも９７％以上の密度比に達したものを用いている。 Table 1 shows the composition list of the sintered bodies subjected to the test in the present example. Here, sample no. D-1 to D-12 show examples of the present invention. C-1 to 4 show the comparative examples. Also, for sample no. D'-2 is the sample No. Derivative example of D-2, sample no. D'-3 is the sample No. Derivation examples of D-3 are respectively shown, and all are included in the embodiments of the present invention. Furthermore, as conventional examples, WC-Co alloy manufactured in-house, and commercially available VC-50 (CIS classification) alloy, Ni-Ir super alloy and silicon nitride (Si 3 N 4 ) were used as sample Nos. N-1 to 4 respectively. Here, the composition of the hard phase is described as a total of 100 as% by mass. In addition, the composition of the metal bonding phase is described as a total of 100 as atomic percent. Furthermore, the ratio of the metal bonding phase to the entire sintered body is expressed as volume%. In addition, as for all the materials of the present example, a material having a density ratio of at least 97% or more as a result of evaluation using the Archimedes method with respect to the theoretical density derived by the mixing rule of the composition is used.

ここで、焼結体に対する硬質相の粒径や金属結合相の割合（体積比）は、走査型電子顕微鏡及び電子線マイクロアナライザーを用いて評価することが可能である。走査型電子顕微鏡によって観察された試料Ｎｏ．Ｄ−１の反射電子像を図２に示す。図２では、明るい灰色部は硬質相を形成するＷＣによって、濃い灰色部は金属結合相を形成するＮｉとＡｌによってそれぞれ構成されている。   Here, the particle size of the hard phase to the sintered body and the ratio (volume ratio) of the metal bonding phase can be evaluated using a scanning electron microscope and an electron beam microanalyzer. Sample No. 1 observed by a scanning electron microscope. The reflection electron image of D-1 is shown in FIG. In FIG. 2, the light gray part is constituted by WC which forms a hard phase, and the dark gray part is respectively constituted by Ni and Al which form a metal bonding phase.

硬質相の粒径に関しては、電子顕微鏡像を基に、切断法に準じて、観察像に任意の直線を複数本引き、硬質相粒子と交わる直線の長さの総和を、直線と交わる硬質相粒子の総数で除して求める方法を用いて評価した。その結果、図２の試料Ｎｏ．Ｄ−１では、硬質相粒子（ＷＣ）の粒径は１．２μｍと見積もられた。また、それと同様の測定方法によって評価された試料Ｎｏ．Ｄ−２〜１２の硬質相粒子（ＷＣ）の粒径についても、何れも１．０〜１．５μｍの範囲で見積もられた。このことから、本実施例の硬質相粒子（ＷＣ）は、超硬工具協会規格（ＣＩＳ０１９Ｄ−２００５）の材料規格の２桁目の分類に当てはめると、「Ｍ」（１．０〜２．５μｍ）に相当する粒径を有するものと推察される。 With regard to the particle diameter of the hard phase, a plurality of arbitrary straight lines are drawn in the observation image according to the cutting method based on the electron microscope image, and the total length of straight lines intersecting the hard phase particles intersects the straight line Evaluation was made using the method of dividing by the total number of particles. As a result, the sample No. 1 in FIG. At D-1, the particle size of hard phase particles (WC) was estimated to be 1.2 μm. Moreover, the sample No. 4 evaluated by the measurement method similar to it. The particle sizes of D-2 to 12 hard phase particles (WC) were also estimated in the range of 1.0 to 1.5 μm. From this, the hard phase particles (WC) of the present example are “M” (1.0 to 2.5 μm) when applied to the second digit classification of the material standards of the Carbide Tools Association Standard (CIS 019 D-2005). Is presumed to have a particle size corresponding to.

また、前記金属結合相の割合（体積比）に関しては、電子顕微鏡像を基に、画像処理法によって減色或いは２値化する方法を用いて評価した。その結果、それらの存在比から算出される硬質相と金属結合相との体積比は、秤量時の配合比から算出される体積比と良い一致を示し、試料Ｎｏ．Ｄ−１では１５体積％と見積もられた。また、それと同様の測定方法によって評価された試料Ｎｏ．Ｄ−２〜１２における硬質相と金属結合相との体積比についても、秤量時の配合比から算出される体積比と良い一致を示した。このことから、表１に示す金属結合相の体積比は、秤量時の配合比を基に算出した値を記載している。また、硬質相及び金属結合相の組成に関しても、秤量時の配合比を基に算出した値を記載している。   Further, the ratio (volume ratio) of the metal bonding phase was evaluated using a method of reducing color or binarizing by an image processing method based on an electron microscope image. As a result, the volume ratio of the hard phase to the metal bonding phase calculated from the abundance ratio of them shows good agreement with the volume ratio calculated from the compounding ratio at the time of weighing. It was estimated to be 15% by volume at D-1. Moreover, the sample No. 4 evaluated by the measurement method similar to it. The volume ratio of the hard phase to the metal bonding phase in D-2 to 12 also showed good agreement with the volume ratio calculated from the compounding ratio at the time of weighing. From this, the volume ratio of the metal bonding phase shown in Table 1 describes the value calculated based on the compounding ratio at the time of weighing. In addition, with regard to the compositions of the hard phase and the metal bonding phase, values calculated based on the compounding ratio at the time of weighing are described.

次に、試験に供した焼結体が有する金属結合相の組織、機械特性、及び摩擦攪拌工程後の回転工具３の状態をまとめた一覧をそれぞれ表２，３に示す。 Next, Tables 2 and 3 respectively show a list of the structure of the metal bonding phase of the sintered body subjected to the test, the mechanical properties, and the state of the rotary tool 3 after the friction stirring step.

本発明における金属結合相内のＬ１２相（γ’相）及びＢ２相（β相）の有無は、Ｃｕ−Ｋα線源を用いたＸ線回折法による測定結果に基づき定義される。そして、それらの体積比は、これらの回折ピークを基にＰＤＦデータベース中の参照強度比（ＲＩＲ：Ｒｅｆｅｒｅｎｃｅ Ｉｎｔｅｎｓｉｔｙ Ｒａｔｉｏ）を利用することによって得られる各々の成分の存在比（重量比）から算出される。ここで、局所的にみると、硬質相を形成するＷＣ等が結合相へ固溶することによりＣ原子が侵入し、一部がＥ２１相になると考えられる。一方で、結合相全体でみると、Ｌ１２相（γ’相）中の八面***置の一部に、Ｃ原子が侵入型原子として配置されたＬ１２相（γ’相）であるとみなせる。そのため、元素分析により結合相中にＣ原子の存在が認められても、本発明ではＬ１２相（γ’相）に相当するものとして扱っている。 The presence or absence of the L1 2 phase (γ 'phase) and the B2 phase (β phase) in the metal bonding phase in the present invention is defined based on the measurement results by the X-ray diffraction method using a Cu-Kα radiation source. Then, their volume ratio is calculated from the abundance ratio (weight ratio) of each component obtained by using the reference intensity ratio (RIR: Reference Intensity Ratio) in the PDF database based on these diffraction peaks. . Here, the locally viewed, the C atoms to penetrate by WC or the like to form a hard phase forms a solid solution to the binding phase, considered part becomes E2 1 phase. On the other hand, looking at the total binding phases, regarded as L1 2 phase (gamma is 'part of the octahedral sites in phase), L1 2 phase in which C atoms are arranged as interstitial atoms (gamma' phase) . Therefore, even if the presence of C atoms was observed in the binding phase by elemental analysis, the present invention is treated as equivalent to L1 2 phase (gamma 'phase).

このＸ線回折法を用いた評価の例として、試料Ｎｏ．Ｄ−２及び試料Ｎｏ．Ｃ−４のＸ線回折プロファイルを図３に示す。ここで、試料Ｎｏ．Ｄ−２で確認できる回折ピークはＷＣとＬ１２相（γ’相）を形成するＮｉ３Ａｌのみであるが、試料Ｎｏ．Ｃ−４では、それらの回折ピーク加えて、Ｂ２相（β相）を形成するＮｉＡｌの回折ピークも確認できる。そして、結合相中の存在比を上述した参照強度比から算出すると、試料Ｎｏ．Ｄ−２では、Ｌ１２相（γ’相）がほぼ１００体積％相当であるのに対して、試料Ｎｏ．Ｃ−４では、Ｌ１２相（γ’相）とＢ２相（β相）とが７５：２５（体積比）の割合で存在すると算出される。 As an example of evaluation using this X-ray diffraction method, sample No. D-2 and sample nos. The X-ray diffraction profile of C-4 is shown in FIG. Here, sample no. The diffraction peak which can be confirmed by D-2 is only Ni 3 Al which forms WC and L1 2 phase (γ ′ phase). In C-4, those diffraction peaks can be added, and also the diffraction peaks of NiAl forming the B2 phase (β phase) can be confirmed. Then, when the abundance ratio in the binder phase is calculated from the above-described reference intensity ratio, the sample No. 1 is obtained. In D-2, while the L1 2 phase (γ ′ phase) is equivalent to almost 100% by volume, sample No. In C-4, it is calculated that the L1 2 phase (γ 'phase) and the B2 phase (β phase) are present at a ratio of 75:25 (volume ratio).

なお、本実施例における焼結体のＬ１２相（γ’相）には、Ｃｕ−Ｋα線源を用いた測定において、Ａ１相（γ相）にはない２４．８°付近の（１００）面の回折ピークの発現が認められる。また、本実施例における焼結体の構造的な特徴としては、（１１１）面の回折ピークが約４３．５°〜４３．９°の範囲で発現しており、Ｎｉを金属結合相としたＷＣ−Ｎｉ基合金におけるＡ１相（γ相）の（１１１）面の回折ピークの範囲である約４４．０°〜４４．３°よりも、かなり低角側に発現していることが挙げられる。 In the L1 2 phase (γ 'phase) of the sintered body in this example, (100) around 24.8 ° which is not in A1 phase (γ phase) in measurement using a Cu-Kα radiation source The appearance of diffraction peaks on the surface is observed. Moreover, as a structural feature of the sintered body in the present example, the diffraction peak of (111) plane appears in the range of about 43.5 ° to 43.9 °, and Ni is used as the metal bonding phase. It can be mentioned that it is expressed at a considerably lower angle side than about 44.0 ° to 44.3 ° which is the range of the diffraction peak of the (111) plane of A1 phase (γ phase) in WC-Ni base alloy .

また、表２において、室温における硬さ（ＨＲＡ）は、ロックウェル硬さ試験機によって、表中「強度」で示される曲げ強度は、インストロン型万能試験機を用いた３点曲げ試験によって評価を実施している。そして、破壊靭性は、ビッカース圧子による評価法である圧子圧入法（ＩＦ：Ｉｎｄｅｎｔａｔｉｏｎ Ｆｒａｃｔｕｒｅ法）を用いて評価している。各々の評価は、焼結体を長さ４０ｍｍ・幅５ｍｍ・厚み１．５ｍｍの角棒状に加工し、更に両面を３〜５μｍのダイヤモンドを用いて鏡面加工を施した試料にて行っている。更に、高温硬さ（ＨＶ）は、高温ビッカース硬さ測定システム（ＡＶＫ−ＨＦ）を用いて評価している。ここで、圧子と試料との温度差に伴う硬さ測定値の誤差を低減させるため、各温度における測定前に、５分以上、試料面と圧子とを接触させ続けることによって、圧子を加熱した後に測定を行っている。   In Table 2, hardness at room temperature (HRA) is evaluated by Rockwell hardness tester, and bending strength indicated by "strength" in the table is evaluated by three-point bending test using Instron universal tester. Have been implemented. And fracture toughness is evaluated using the indenter indentation method (IF: Indentation Fracture method) which is an evaluation method by a Vickers indenter. Each evaluation is performed on a sample obtained by processing a sintered body into a square rod having a length of 40 mm, a width of 5 mm, and a thickness of 1.5 mm and further mirror-finishing both surfaces using diamond of 3 to 5 μm. Furthermore, high temperature hardness (HV) is evaluated using a high temperature Vickers hardness measurement system (AVK-HF). Here, the indenter was heated by continuing the contact between the sample surface and the indenter for 5 minutes or more before measurement at each temperature in order to reduce the error in the hardness measurement value due to the temperature difference between the indenter and the sample. I am doing measurement later.

本実施例における回転工具３は、放電加工及び切断・研削等の機械加工を用いて以下の形状に成形したものを使用している。
・ショルダ：端面の外周縁部を曲率半径１ｍｍのＲ加工を施した直径１２ｍｍの円柱
・プローブ：ショルダ５の端面中央から軸方向に突設した球冠（球面をそれと交わる平面で切りとった部分）であり、底部直径４ｍｍ、高さ０．８ｍｍ、曲率半径１．７ｍｍ As the rotary tool 3 in the present embodiment, one formed into the following shape using machining such as electric discharge machining and cutting / grinding is used.
・ Shoulder: A 12 mm diameter cylinder with a radius of curvature of 1 mm on the outer peripheral edge of the end face ・ Probe: A spherical crown axially projecting from the center of the end face of shoulder 5 (a part of the spherical surface cut off in a plane intersecting with it) Bottom diameter 4 mm, height 0.8 mm, radius of curvature 1.7 mm

図１に示す回転工具３を用いた摩擦攪拌工程による加工試験においては、被加工材として、ＳＵＳ４３０からなる厚み１ｍｍの圧延板（硬さ評価値：ＨＶ２３０〜２７０）を使用した。そして、この圧延板を２枚重ねて２ｍｍ相当の厚みとしたうえで、軟鋼性で厚み１０ｍｍのバックプレート６上に乗せることにより、装置のステージに固定した。   In the processing test by the friction stirring process using the rotary tool 3 shown in FIG. 1, a 1 mm-thick rolled plate (hardness evaluation value: HV 230 to 270) made of SUS 430 was used as a workpiece. Then, two of the rolled plates were stacked to have a thickness of 2 mm, and the plate was fixed on the stage of the apparatus by placing it on a back plate 6 having a thickness of 10 mm and being mild steel.

そして、設定荷重１ｔｏｎ、最大挿入深さ１．５ｍｍ、工具回転数１８００ｒｐｍ、Ａｒガスフロー２５Ｌ／ｍｉｎを共通の設定条件としたうえで、以下の２つの異なる条件を用いて加工試験を実施した。１つ目の条件は、回転工具の移動速度を１００ｍｍ／ｍｉｎ、加工距離１００ｍｍとし、これを「条件１」とした。２つ目の条件は、回転工具の移動速度を１０００ｍｍ／ｍｉｎ、距離２００ｍｍ刻みで合計１ｍを加工する条件とし、これを「条件２」とした。このとき、被加工材と回転工具外周との間に発生する摩擦熱は、放射温度計による概算として「条件１」において１０５０℃前後、「条件２」において９２０℃前後と見積もられた。なお、ここで「条件１」及び「条件２」の２つ条件を設定しているのは、「条件２」の下で良好な試験結果が得られた各試料（回転工具３）につき、より高温条件下における耐熱性を「条件１」によって評価するためである。   Then, with the setting load 1 ton, the maximum insertion depth 1.5 mm, the tool rotational speed 1800 rpm, and the Ar gas flow 25 L / min as common setting conditions, the processing test was performed using the following two different conditions. The first condition is that the moving speed of the rotary tool is 100 mm / min, and the processing distance is 100 mm, which is referred to as “condition 1”. The second condition is that the moving speed of the rotary tool is 1000 mm / min, and a total of 1 m is machined at intervals of 200 mm, which is referred to as “condition 2”. At this time, the frictional heat generated between the workpiece and the outer periphery of the rotary tool was estimated to be around 1050 ° C. under “condition 1” and around 920 ° C. under “condition 2” as an approximation by the radiation thermometer. Here, the two conditions of “condition 1” and “condition 2” are set for each sample (rotary tool 3) for which a good test result was obtained under “condition 2”. It is in order to evaluate the heat resistance under high temperature conditions by "condition 1".

ここで、被加工材表面の加工状態に関する例として、「条件２」にて加工した後の被加工材の外観を図４〜６に示す。図４に示した接合部を拡大すると、通常は図５に示す外観を有するが、加工欠陥が発生すると、接合部の一部或いは全体に図６に示すような空孔が発生する。この空孔の発生が認められた場合に、加工欠陥有りとした。   Here, the appearance of the workpiece after processing under “condition 2” is shown in FIGS. 4 to 6 as an example regarding the processing state of the surface of the workpiece. When the joint shown in FIG. 4 is enlarged, it usually has the appearance shown in FIG. 5, but when a processing defect occurs, a void as shown in FIG. 6 is generated in part or all of the joint. It was considered that there was a processing defect when the generation of this void was recognized.

加工試験後の回転工具３のプローブ４及びショルダ５の摩耗量は、触針式形状測定器を用いて回転工具先端の断面形状の変化を計測することによって評価した。プローブ４の摩耗量はその先端部の寸法減少量の最大値で表し、ショルダ５の摩耗量はその両端部に存在する寸法減少量の最も少ない部位の２点平均値で表した。例えば、「条件２」によって試験を実施した試料Ｎｏ．Ｄ−２及び試料Ｎｏ．Ｎ−４の断面形状をそれぞれ示した図７，８において、灰色部が試験前の断面形状を示し、黒色部が試験後の断面形状を示している。この場合、試料Ｎｏ．Ｄ−２はプローブ摩耗量０．００９ｍｍ，ショルダ摩耗量０．０３７ｍｍであり、試料Ｎｏ．Ｎ−４はプローブ摩耗量０．００１ｍｍ，ショルダ摩耗量０．０６９ｍである。   The amount of wear of the probe 4 and the shoulder 5 of the rotary tool 3 after the processing test was evaluated by measuring a change in cross-sectional shape of the rotary tool tip using a stylus type shape measuring instrument. The amount of wear of the probe 4 is represented by the maximum value of the amount of dimensional reduction of its tip, and the amount of wear of the shoulder 5 is represented by the two-point average value of the portions with the smallest amount of dimensional reduction present at both ends. For example, for the sample No. 1 in which the test was performed under “condition 2”. D-2 and sample nos. In FIGS. 7 and 8 respectively showing the cross-sectional shape of N-4, the gray part shows the cross-sectional shape before the test, and the black part shows the cross-sectional shape after the test. In this case, sample no. Sample No. D-2 has a probe wear amount of 0.009 mm and a shoulder wear amount of 0.037 mm. N-4 has a probe wear amount of 0.001 mm and a shoulder wear amount of 0.069 m.

回転工具３の良否は、耐熱性の差異に大きく関わる「ショルダ変形」と、接合の信頼性に関わる「被加工材表面に発生した加工欠陥」で判断している。「ショルダ変形」と「被加工材表面に発生した加工欠陥」の両方が「無し」と判断された場合に本発明の効果を奏する良品であると判定している。特に「ショルダ変形」の有無に関しては、本実施例における優劣に留まらず、本発明の本質的な耐熱性の優劣を示唆しているため非常に重要である。   The quality of the rotating tool 3 is judged by "shoulder deformation" which is largely related to the difference in heat resistance, and "processing defect generated on the surface of the workpiece" which is related to the reliability of bonding. It is determined that the product is a non-defective product exhibiting the effects of the present invention when it is determined that both “shoulder deformation” and “process defect generated on the surface of the workpiece” are “absent”. In particular, with respect to the presence or absence of the "shoulder deformation", it is very important not only because of the superiority or inferiority in the present example, but also because it suggests the superiority or inferiority of the essential heat resistance of the present invention.

ここで、ショルダ変形（クリープ）に関して、分かりやすい極端な例として、表１に記載しない内製のＷＣ−２０Ｃｏ合金によって作製した回転工具を使用し、「条件１」の下で試験を実施した後の外観を図９に示す。この外観から明らかな通り、摩擦熱によりショルダ上端部が大きく潰れて、その外周側面が外側に膨出するため、その外径が大きく変化していることが判る。そこで、ここでの試験においては、ショルダの上端部における最大外径Ｓと、そこから軸方向基端側（プローブ４が突設された端面とは逆側）に１ｍｍ離れた部位におけるショルダの外径Ｔとを投影機で測定し、それらの差Ｓ−Ｔと前記外径Ｔとの比で表される外径変化率が１．０％を超えた場合に「変形有り」としている（なお、図９の外径変化率は６．３％である）。   Here, with regard to shoulder deformation (creep), after performing a test under “condition 1”, using a rotary tool made of an internally manufactured WC-20Co alloy not listed in Table 1 as an intelligible extreme example The appearance of is shown in FIG. As apparent from this appearance, the upper end of the shoulder is largely crushed by the frictional heat, and the outer peripheral side surface bulges outward, so it can be seen that the outer diameter is largely changed. Therefore, in the test here, the maximum outer diameter S at the upper end portion of the shoulder and the outside of the shoulder at a position 1 mm away from the base end side in the axial direction (opposite to the end face where the probe 4 is provided) The diameter T is measured by a projector, and when the rate of change in outer diameter represented by the ratio of the difference S-T to the outer diameter T exceeds 1.0%, it is regarded as "deformed". , Outer diameter change rate of FIG. 9 is 6.3%).

上記の表３に示すように、本発明の実施例である試料Ｎｏ．Ｄ−１〜１２は、摩擦攪拌工程後における『「条件１」でのショルダ変形（クリープ）』の外径変化率が何れも１．０％以下であり、それに関連して、これら試料のプローブ及びショルダの摩耗量が、比較例及び従来材の例に示した各材料よりも有意に少ない傾向を示していることが判る。   As shown in Table 3 above, sample No. 1 which is an example of the present invention. In D-1 to D-12, the rate of change in the outer diameter of “shoulder deformation (creep) under“ condition 1 ”” after the friction stirring step is all 1.0% or less, and related thereto, the probes of these samples It can be seen that the wear amount of shoulder and shoulder tend to be significantly smaller than those of the comparative examples and the conventional materials.

そこでまず、硬質相の組成かつ金属結合相の組成が共通している試料Ｎｏ．Ｄ−１，２，３及び試料Ｎｏ．Ｃ−１，２について比較する。表２に示されるように、これら試料の違いは、焼結体全体に対する金属結合相の割合（体積％）であり、割合が少ない順に、Ｎｏ．Ｃ−１（８体積％）＜Ｎｏ．Ｄ−１（１５体積％）＜Ｎｏ．Ｄ−２（３０体積％）＜Ｎｏ．Ｄ−３（５５体積％）＜Ｎｏ．Ｃ−２（７０体積％）となっている。   Therefore, first, sample No. 1 in which the composition of the hard phase and the composition of the metal bonding phase are common. D-1, 2, 3 and sample nos. It compares about C-1 and 2. As shown in Table 2, the difference between these samples is the ratio (volume%) of the metal bonding phase to the whole sintered body, and in order of decreasing ratio, No. 1 C-1 (8% by volume) <No. D-1 (15% by volume) <No. D-2 (30% by volume) <No. D-3 (55 volume%) <No. It is C-2 (70 volume%).

金属結合相の割合が８体積％と少ない試料Ｎｏ．Ｃ−１では、回転工具３が被加工材へ挿入している途中の段階で破砕してしまい、試験の継続が不可能であった。これは、金属結合相の割合を低減させることによって極めて優れた高温硬さを示す一方、破壊靭性が５ＭＰａ・ｍ１／２であり、セラミックスである窒化珪素Ｎｏ．Ｎ−４と比較しても有意に低いことに起因する。それに対して、金属結合相の割合が１５体積％に達した試料Ｎｏ．Ｄ−１は、窒化珪素Ｎｏ．Ｎ−４を超える破壊靭性を有し、摩擦攪拌による加工試験でも良好な結果が得られた。以上のことから、本発明における焼結体に必要な金属結合相の割合は少なくとも１５体積％以上と定められる。 Sample No. 1 in which the proportion of the metal bonding phase is as small as 8% by volume. In C-1, the rotary tool 3 was crushed in the middle of being inserted into the workpiece, and the test could not be continued. This shows extremely excellent high temperature hardness by reducing the proportion of the metal bonding phase, while the fracture toughness is 5 MPa · m 1/2 , and silicon nitride No. 4 which is a ceramic is used. It results from being significantly lower than N-4. On the other hand, sample No. 1 in which the proportion of the metal bonding phase reached 15% by volume. D-1 is a silicon nitride no. The fracture toughness was higher than N-4, and good results were obtained even in processing tests by friction stirring. From the above, the proportion of the metal bonding phase required for the sintered body in the present invention is determined to be at least 15% by volume or more.

但し、金属結合相の割合を増やすほど、破壊靭性は向上する一方で高温硬さは低減する。金属結合相の割合が５５体積％の試料Ｎｏ．Ｄ−３まではショルダ変形（クリープ）による外径変化率は１．０％以下であったが、金属結合相の割合が７０体積％と多い試料Ｎｏ．Ｃ−２では、摩擦攪拌による加工後のプローブ４及びショルダ５の摩耗量が大きく、ショルダ変形（クリープ）による外径変化率も１．０％を超えて１．３％に達する。以上から、耐熱性の確保のために、本発明における焼結体に必要な金属結合相の割合は５５体積％以下と定められる。   However, as the proportion of the metal bonding phase is increased, the fracture toughness is improved while the high temperature hardness is reduced. Sample No. 5 in which the proportion of the metal bonding phase is 55% by volume. Although the outer diameter change rate by shoulder deformation (creep) was 1.0% or less to D-3, sample No. 1 in which the percentage of the metal bonding phase was as large as 70% by volume. In C-2, the wear amount of the probe 4 and the shoulder 5 after processing by friction stirring is large, and the outer diameter change rate due to shoulder deformation (creep) also exceeds 1.0% and reaches 1.3%. From the above, the proportion of the metal bonding phase necessary for the sintered body in the present invention is determined to be 55% by volume or less in order to ensure the heat resistance.

なお、硬質相が含まれていない、実質的にＬ１２相（γ’相）を含む金属結合相のみで形成されているとみなせる市販の試料Ｎｏ．Ｎ−３（Ｎｉ−Ｉｒ超合金）では、「条件１」及び「条件２」の何れにおいても、被加工材の接合開始後すぐに被加工材の表面に加工欠陥（空孔）が発生したため、何れも５０ｍｍで試験を中断した。使用後の回転工具は、プローブ４が完全に消失していた。「条件１」によって試験を実施した試料Ｎｏ．Ｎ−３の工具先端部の外観を図１０に示す。この図１０から分かるように、短い距離ながらショルダ５のクリープ変形の痕跡がないことから、この試料Ｎｏ．Ｎ−３は、硬質相が存在しないにもかかわらず優れた耐熱性を有しているものと推察される。しかしながら、プローブ４は、ショルダ５と被加工材との摩擦熱が十分に発生するより前に接触する部位であり、低い温度の状態から被加工材の塑性変形を伴う大きな圧力で摺動させる必要がある。このことから、被加工材と回転工具３との硬度差をより大きくするための硬質相の存在が必要不可欠であることが分かる。 In addition, commercially available sample No. 1 which can be considered to be formed only of the metal bonding phase substantially including the L1 2 phase (γ ′ phase) which does not contain the hard phase. In N-3 (Ni-Ir super alloy), processing defects (voids) were generated on the surface of the workpiece immediately after the start of bonding of the workpiece under both “condition 1” and “condition 2”. All stopped the test at 50 mm. The rotary tool after use had the probe 4 completely disappeared. Sample No. 1 for which the test was performed under “condition 1”. The appearance of the N-3 tool tip is shown in FIG. As can be seen from FIG. 10, there is no evidence of creep deformation of shoulder 5 over a short distance. N-3 is presumed to have excellent heat resistance despite the absence of a hard phase. However, the probe 4 is a portion which comes in contact with the shoulder 5 before the frictional heat of the workpiece 5 is sufficiently generated, and it is necessary to slide the workpiece 4 under a large pressure accompanied by plastic deformation of the workpiece from a low temperature state. There is. From this, it can be seen that the presence of a hard phase for increasing the difference in hardness between the workpiece and the rotary tool 3 is essential.

次に、硬質相の組成と金属結合相の割合が共通している試料Ｎｏ．Ｄ−２，４，５，６と試料Ｎｏ．Ｃ−３，４とを比較する。これらの試料は、金属結合相に存在するＡｌの量が、大凡２５原子％を境として、それよりも少ない場合の第１パターンと、それよりも多い場合の第２パターンとに、大きく二分される。   Next, sample No. 1 in which the composition of the hard phase and the proportion of the metal bonding phase are common. D-2, 4, 5, 6 and sample nos. Compare C-3,4. These samples are largely divided into a first pattern in which the amount of Al present in the metal bonding phase is less than approximately 25 atomic percent, and a second pattern in which the amount is higher than that. Ru.

まず、前記第１パターンにおける違いは、金属結合相の組成（Ａｌの割合）の変化に起因した金属間化合物Ｌ１２相（γ’相）の割合（体積％）である。その割合が少ない順に、Ｎｏ．Ｃ−３（２５体積％）＜Ｎｏ．Ｄ−５（４０体積％）＜Ｎｏ．Ｄ−４（６０体積％）＜Ｎｏ．Ｄ−２（〜１００体積％）となっており、金属結合相におけるＡｌの割合（原子％）がより大きいほど、Ｌ１２相（γ’相）の割合もより大きくなっている。 First, the difference in the first pattern is the ratio (volume%) of the intermetallic compound L1 2 phase (γ ′ phase) caused by the change in the composition (ratio of Al) of the metal bonding phase. In the ascending order of the ratio, No. C-3 (25% by volume) <No. D-5 (40% by volume) <No. D-4 (60% by volume) <No. D-2 has a (100 vol%), the proportion of Al in the metal binder phase (atomic%) Gayori larger, is greater and more even rate of L1 2 phase (gamma 'phase).

金属結合相中のＬ１２相（γ’相）の割合が２５体積％と少ない試料Ｎｏ．Ｃ−３では、摩擦攪拌による加工後のプローブ４及びショルダ５の摩耗量がやや大きく、ショルダ変形（クリープ）による外径変化率も１．０％を超えて２．５％に達しており、また、被加工材の表面にも微細な加工欠陥（空孔）が発現している。それに対して、Ｌ１２相（γ’相）の割合が４０体積％以上の試料Ｎｏ．Ｄ−２，４，５では、何れもショルダ変形（クリープ）による外径変化率が１．０％以下を示し、被加工材の表面の加工欠陥（空孔）も見られない。以上のことから、耐熱性の確保のために、本発明における焼結体に必要な金属結合相中のＬ１２相（γ’相）の割合は４０体積％以上と定められる。 Sample No. 1 in which the proportion of L1 2 phase (γ ′ phase) in the metal bonding phase is as small as 25% by volume. In C-3, the wear amount of probe 4 and shoulder 5 after processing by friction stirring is slightly large, and the rate of change in outer diameter due to shoulder deformation (creep) also exceeds 1.0% and reaches 2.5%, In addition, fine processing defects (voids) appear on the surface of the workpiece. On the other hand, the sample No. 1 in which the proportion of L1 2 phase (γ ′ phase) is 40 vol% or more In each of D-2, 4, and 5, the outer diameter change rate due to shoulder deformation (creep) shows 1.0% or less, and no processing defect (void) on the surface of the workpiece is observed. From the above, in order to ensure the heat resistance, the proportion of L1 2 phase (γ ′ phase) in the metal bonding phase necessary for the sintered body in the present invention is determined to be 40% by volume or more.

なお、金属結合相中にＬ１２相（γ’相）が存在しない従来のＷＣ基合金であるＮｏ．Ｎ−１，２は、何れもショルダ変形（クリープ）による外径変化率が１．０％を超えていることから、本発明の試料Ｎｏ．Ｄ−１〜１２及び試料Ｎｏ．Ｄ’−２，３と比較して耐熱性に乏しいと判断される。 In addition, No. 1 which is a conventional WC base alloy in which the L1 2 phase (γ ′ phase) does not exist in the metal bonding phase. Since the outer diameter change rate by shoulder deformation (creep) of each of N-1 and 2 exceeded 1.0%, sample No. 1 of the present invention was obtained. D-1 to 12 and sample Nos. It is judged that heat resistance is poor compared with D'-2, 3.

次に、前記第２パターンにおける違いは、金属結合相の組成（Ａｌの割合）の変化に起因した金属間化合物Ｂ２相（β相）の割合（体積％）である。その割合が少ない順に、Ｎｏ．Ｄ−２（０体積％）＜Ｎｏ．Ｄ−６（１０体積％）＜Ｎｏ．Ｃ−４（２５体積％）となっており、金属結合相におけるＡｌの割合（原子％）がより大きいほど、Ｂ２相（β相）の割合の割合もより大きくなっている。   Next, the difference in the second pattern is the ratio (volume%) of the intermetallic compound B2 phase (β phase) caused by the change in the composition (ratio of Al) of the metal bonding phase. In the ascending order of the ratio, No. D-2 (0% by volume) <No. D-6 (10% by volume) <No. C-4 (25% by volume), and the larger the proportion (atomic%) of Al in the metal bonding phase, the larger the proportion of the proportion of the B2 phase (β phase).

金属結合相中のＢ２相（β相）の割合が１０体積％である試料Ｎｏ．Ｄ−６では、ショルダ変形（クリープ）による外径変化率が１．０％以下を示し、被加工材の表面にも加工欠陥（空孔）は見られなかった。それに対して、金属結合相中のＢ２相（β相）の割合がより多い２５体積％である試料Ｎｏ．Ｃ−４では、回転工具を被加工材へ挿入している途中の段階で破砕してしまい、試験の継続が不可能であった。これは、金属結合相中のＢ２相（β相）が増えると、硬さが向上する一方、破壊靭性が著しく低下することに起因している。以上のことから、本発明における焼結体を構成する金属結合相中のＢ２相（β相）の体積比は、１０体積％以下とする必要があるといえる。更に、本発明の効果を最大限に発揮させるためには、試料Ｎｏ．Ｄ−６を除いた他の実施例の試料のように、Ｘ線回折装置の検出限界未満とすることがより好ましい。ここで、Ｘ線回折装置の検出限界未満とは、９ｋＷ級の高出力Ｘ線回折装置であっても安定した有無の検出が困難となる５体積％未満とする。   Sample No. 1 in which the proportion of B2 phase (β phase) in the metal bonding phase is 10% by volume. In D-6, the rate of change in outer diameter due to shoulder deformation (creep) was 1.0% or less, and no processing defects (voids) were observed on the surface of the workpiece. On the other hand, Sample No. 1 in which the proportion of B2 phase (β phase) in the metal bonding phase is 25 vol% is higher. In C-4, the rotating tool was crushed in the middle of inserting into the workpiece, and the test could not be continued. This is attributed to the fact that when the B2 phase (β phase) in the metal bonding phase is increased, the hardness is improved while the fracture toughness is significantly reduced. From the above, it can be said that the volume ratio of B2 phase (β phase) in the metal bonding phase constituting the sintered body in the present invention needs to be 10 volume% or less. Furthermore, in order to maximize the effects of the present invention, sample no. As in the samples of the other examples except D-6, it is more preferable to set the value below the detection limit of the X-ray diffractometer. Here, “less than the detection limit of the X-ray diffraction device” is less than 5% by volume where detection of the presence or absence of stability is difficult even with a high-power X-ray diffraction device of 9 kW class.

以上の結果は、金属結合相中に含まれるＡｌの割合が、結合相の組織に占めるＬ１２相（γ’相）及びＢ２相（β相）の割合に対して大きな影響を与えていることを示唆する。すなわち、金属結合相中に含まれるＡｌの割合を増減させることにより、結合相の組織に占めるＬ１２相（γ’相）及びＢ２相（β相）の割合を調節することができることが分かる。 The above results show that the proportion of Al contained in the metal bonding phase has a large influence on the proportion of L1 2 phase (γ 'phase) and B2 phase (β phase) in the structure of the bonding phase Suggest. That is, it is understood that the proportions of the L1 2 phase (γ ′ phase) and the B2 phase (β phase) in the structure of the binder phase can be adjusted by increasing or decreasing the proportion of Al contained in the metal binder phase.

ところで、金属結合相を形成する原料粉末であるＡｌは極めて酸化しやすいことから、不純物として焼結体中に酸化物が混入することを防ぐことは極めて困難である。極端な例であるが、焼結体中の全Ａｌ量の２０％相当が酸化した場合、試料Ｎｏ．Ｄ−２では大よそ３体積％に相当する酸化物が混入することになる。酸化物の混入に対する影響を検討するため、試料Ｎｏ．Ｄ−２の組成を基に原料粉末の全Ａｌ量の２０％相当をＡｌ２Ｏ３に置換した試料Ｎｏ．Ｄ’−２を作製した。なお、この場合のＡｌ２Ｏ３の混入量は２．６モル％に相当し、金属成分としてのＡｌの減少量は４．５原子％に相当する。 By the way, since Al which is a raw material powder which forms a metal binding phase is extremely easily oxidized, it is extremely difficult to prevent the oxide from being mixed in the sintered body as an impurity. As an extreme example, when 20% equivalent of the total amount of Al in the sintered body is oxidized, sample No. 1 is obtained. In D-2, an oxide equivalent to about 3% by volume is mixed. In order to examine the influence on the mixing of oxides, sample No. Sample No. 1 in which 20% equivalent of the total Al content of the raw material powder was substituted by Al 2 O 3 based on the composition of D-2. D'-2 was produced. In this case, the mixing amount of Al 2 O 3 corresponds to 2.6 mol%, and the reduction amount of Al as a metal component corresponds to 4.5 atomic%.

試料Ｎｏ．Ｄ’−２は、ショルダ変形（クリープ）による外径変化率が１．０％以下を示し、被加工材の表面の加工欠陥も見られないため、本発明の実施例として良好な効果を奏すると判断される。一方で、この試料Ｎｏ．Ｄ’−２は、試料Ｎｏ．Ｄ−２と比較して、破壊靭性等の機械特性において若干の低下傾向を示していることが分かる。以上のことから、本発明の効果を最大限に発揮させるためには、保管状態や焼成条件に留意し、出来得る限り酸化物の混入を抑制すること、具体的には、３体積％を超える酸化物の混入を防ぐことが好ましい。   Sample No. D'-2 has an outer diameter change rate of 1.0% or less due to shoulder deformation (creep), and no processing defects on the surface of the workpiece are observed. Therefore, a good effect is exhibited as an embodiment of the present invention. It is judged that. On the other hand, this sample No. D'-2 is a sample No. It can be seen that the mechanical characteristics such as fracture toughness show a slight tendency to decrease compared to D-2. From the above, in order to maximize the effects of the present invention, attention should be paid to storage conditions and baking conditions, and the inclusion of oxides is suppressed as much as possible, specifically, more than 3% by volume. It is preferable to prevent the mixing of oxides.

また、本発明の実施例としての試料Ｎｏ．Ｄ−１〜１２、及び比較例としてのＮｏ．Ｃ−１〜４には、全てＢが微量添加されている。以下、Ｂが微量添加されている理由について、結合相の割合が多い試料Ｎｏ．Ｄ−３を基に、同じ組成でＢのみ添加されていない試料Ｎｏ．Ｄ’−３と比較して述べる。   Moreover, sample No. 1 as an example of the present invention. D-1 to 12 and No. 1 as a comparative example. A small amount of B is added to all of C-1 to C-4. Hereinafter, with respect to the reason why a small amount of B is added, sample No. 1 in which the proportion of the binder phase is large is used. Sample No. 1 in which only B was added with the same composition based on D-3. This will be described in comparison with D'-3.

試料Ｎｏ．Ｄ’−３は、ショルダ変形（クリープ）による外径変化率が１．０％以下を示し、被加工材の表面の加工欠陥も見られないため、本発明の実施例として良好な効果を奏していると判断される。一方で、試料Ｎｏ．Ｄ−３及びＤ’−３をそれぞれ２個ずつ用意し、各々の試料について各温度における硬さ（ＨＶ）を測定すると、図１１に示すように、Ｂが添加されていない試料Ｎｏ．Ｄ’−３の方が常温硬さは若干高いが、６００℃付近を境に試料Ｎｏ．Ｄ−３との優劣が逆転し、９００〜１０００℃では数値にして１００程度の有意な硬度差が生じた。すなわち、Ｂの添加は、Ｌ１２相（γ’相）を含む金属結合相の高温時の硬さの向上に寄与することが分かる。以上のことから、本発明の効果を最大限に発揮させるためには、金属結合相の総量に対して０．０４原子％以上のＢを添加することがより好ましい。但し、Ｂの割合が過剰になると硼化物の発生による機械特性の低下が懸念されるため、Ｂの添加は、金属結合相の総量に対して１原子％以下を目安にすることが好ましい。 Sample No. D'-3 has an outer diameter change rate of 1.0% or less due to shoulder deformation (creep), and no processing defects on the surface of the workpiece are observed, so that a good effect is exhibited as an embodiment of the present invention. It is determined that On the other hand, for sample no. When two pieces of D-3 and two pieces of D'-3 are prepared, and the hardness (HV) at each temperature is measured for each sample, as shown in FIG. Although the normal temperature hardness is slightly higher in D'-3, sample No. 3 was not observed at around 600 ° C. The dominance with D-3 was reversed, and a significant hardness difference of about 100 was generated at 900 to 1000 ° C. That is, it is understood that the addition of B contributes to the improvement of the hardness at high temperature of the metal bonding phase including the L1 2 phase (γ ′ phase). From the above, in order to maximize the effects of the present invention, it is more preferable to add 0.04 atomic% or more of B with respect to the total amount of the metal bonding phase. However, if the proportion of B is excessive, the mechanical properties may be lowered due to the generation of boride. Therefore, the addition of B is preferably about 1 at% or less with respect to the total amount of the metal bonding phase.

更に、金属結合相を構成する元素として、必要に応じて、前述したＮｉ，Ａｌ，Ｂ以外の元素を加えることも可能である。例えば、Ｔｉ，Ｍｏ，Ｓｉ，Ｃｏ，Ｃｒ，Ｗ，Ｔａ，Ｎｂ，Ｃ，Ｚｒ，Ｆｅ及びＣｕのうち何れか１つ或いは２つ以上を添加により含有させることができる。   Furthermore, it is also possible to add elements other than the above-mentioned Ni, Al, and B as necessary to constitute the metal bonding phase. For example, one or more of Ti, Mo, Si, Co, Cr, W, Ta, Nb, C, Zr, Fe and Cu can be added by addition.

試料Ｎｏ．Ｄ−７は、試料Ｎｏ．Ｄ−２を基に、主にＡｌの一部をＴｉ，Ｍｏ，Ｓｉに置換するように添加した焼結体である。試料Ｎｏ．Ｄ−７は、試料Ｎｏ．Ｄ−２よりも破壊靭性が向上する傾向を有する。これは、ＴｉやＳｉは余剰なＣと反応することで、またＭｏはＬ１２相（γ’相）内に固溶することで、Ｌ１２相（γ’相）内に固溶するＷＣ及び／或いはＣの量を低減させる効果を発現した結果であるものと推察される。 Sample No. D-7 shows sample No. It is a sintered body added so that a part of Al is mainly substituted to Ti, Mo, and Si based on D-2. Sample No. D-7 shows sample No. The fracture toughness tends to be improved more than D-2. This, Ti and Si are that react with excess C, also Mo is 'by solid solution in the (phase, L1 2 phase (gamma L1 2 phase gamma)' WC and a solid solution in the phase) It is presumed that this is a result of exhibiting the effect of reducing the amount of C.

試料Ｎｏ．Ｄ−８は、試料Ｎｏ．Ｄ−２を基に、Ｎｉ及びＡｌの一部をＣｏ，Ｃｒ，Ｍｏ，Ｗ，Ｔｉ，Ｔａ，Ｎｂ，Ｃ，Ｚｒに置換するように添加した焼結体である。試料Ｎｏ．Ｄ−８は、Ｌ１２相（γ’相）の割合が５０体積％であるが、このＮｏ．Ｄ−８の９００℃における高温硬さ（ＨＶ）は、同割合が６０体積％である試料Ｎｏ．Ｄ−４の９００℃における高温硬さ（ＨＶ）を上回る。したがって、Ｃｏ，Ｃｒ，Ｍｏ，Ｗ，Ｔａ，Ｎｂ，Ｃ，Ｚｒは、Ｌ１２相（γ’相）を含む金属結合相の耐熱性を向上させる効果を有しているものと推察される。 Sample No. D-8 corresponds to sample No. It is a sintered body added so that a part of Ni and Al may be substituted by Co, Cr, Mo, W, Ti, Ta, Nb, C, Zr based on D-2. Sample No. D-8 has a ratio of 50% by volume of the L1 2 phase (γ ′ phase). The high temperature hardness (HV) at 900 ° C. of D-8 is the same as that of sample No. 6 in which the proportion is 60% by volume. It exceeds the high temperature hardness (HV) at 900 ° C of D-4. Therefore, it is presumed that Co, Cr, Mo, W, Ta, Nb, C, and Zr have the effect of improving the heat resistance of the metal bonding phase including the L1 2 phase (γ ′ phase).

また、本発明の耐熱性や機械特性に直接的に寄与しないため表中には例示していないが、Ｃｕの添加は金属結合相中のＮｉとＡｌに作用して焼結密度を安定化させる効果があるため、有用である。   Moreover, although not illustrated in the table because it does not directly contribute to the heat resistance and mechanical properties of the present invention, the addition of Cu acts on Ni and Al in the metal bonding phase to stabilize the sintered density. It is useful because it is effective.

なお、金属結合相中のＬ１２相（γ’相）の割合を確保するために、Ｂを始めとするＴｉ，Ｍｏ，Ｓｉ，Ｃｏ，Ｃｒ，Ｗ，Ｔａ，Ｎｂ，Ｃ，Ｚｒ，Ｆｅ及びＣｕ等、金属結合相中における必須成分のＮｉ及びＡｌを除く添加物は、金属結合相中のＬ１２相（γ’相）の割合が低い試料Ｎｏ．Ｄ−５及び試料Ｎｏ．Ｄ−８の組成範囲内を目安にして調整し、添加することが好ましい。より具体的には、金属結合相を構成する全元素中にＮｉ及び１５原子％以上のＡｌを必ず含ませ、かつ、金属結合相中におけるＮｉを除いた残りの構成元素の合計が１５原子％以上３５原子％以下の範囲内になることを目安にして調整し、添加することが好ましい。 In order to secure the proportion of L1 2 phase (γ 'phase) in the metal bonding phase, Ti, Mo, Si, Co, Cr, W, Ta, Nb, C, Zr, Fe and B including B The additive such as Cu, except the essential components Ni and Al in the metal bonding phase, is a sample No. 1 in which the proportion of the L1 2 phase (γ ′ phase) in the metal bonding phase is low. D-5 and sample nos. It is preferable to adjust and add the composition range of D-8 as a standard. More specifically, Ni and 15 atomic% or more of Al are necessarily included in all elements constituting the metal bonding phase, and the total of the remaining constituent elements excluding Ni in the metal bonding phase is 15 atomic% It is preferable to adjust and add it within the range of 35 atomic% or more as a standard.

以上のように、表２に示した各試料の機械特性によれば、本発明の実施例である試料Ｎｏ．Ｄ−１〜１２、並びに、試料Ｎｏ．Ｄ’−２及びＮｏ．Ｄ’−３は、室温硬さがＨＲＡで８４．５以上、室温曲げ強度が１２００ＭＰａ以上、室温破壊靭性が８ＭＰａ・ｍ１／２以上、かつ９００℃における硬さがＨＶで４５０以上という条件を全て充足しており、これら各機械特性をバランス良く確保している。それに対して、比較例の試料Ｎｏ．Ｃ−１〜４は、それら機械特性の条件の何れかが欠けていることが分かる。よって、室温硬さがＨＲＡで８４．５以上、室温曲げ強度１２００ＭＰａ以上、室温靭性８ＭＰａ・ｍ１／２以上、かつ９００℃における硬さがＨＶ４５０以上という条件を全て充足する焼結体が、好ましい焼結体の目安になる。 As described above, according to the mechanical characteristics of each sample shown in Table 2, sample No. 1 which is an example of the present invention. D-1 to 12, and sample Nos. D'-2 and no. D'-3 has a room temperature hardness of 84.5 or more in HRA, room temperature flexural strength of 1200 MPa or more, room temperature fracture toughness of 8 MPa · m 1/2 or more, and a hardness at 900 ° C. of 450 or more in HV All the requirements are satisfied, and these mechanical characteristics are secured in a well-balanced manner. On the other hand, sample Nos. It is understood that C-1 to C-4 lack any of the conditions of the mechanical characteristics. Therefore, a sintered body that satisfies all the conditions that the room temperature hardness is 84.5 or more in HRA, the room temperature flexural strength 1200 MPa or more, the room temperature toughness 8 MPa · m 1/2 or more, and the hardness at 900 ° C. is HV 450 or more It becomes a standard of a sintered compact.

ところで、本発明の焼結体は、９００〜１０００℃に及ぶ高温での加熱条件下では徐々に黄褐色に変色していく。変色の度合いは結合相量が減少するほど強くなる傾向にある。変色の原因について、Ｘ線回折を用いて分析した結果を図１２に示す。この分析結果によれば、変色部分に発生した析出相はＷＯ３とＮｉＷＯ４であることから、主にＷＣの酸化が、この変色の支配的な要因であることが分かる。 By the way, the sintered body of the present invention gradually turns to yellow-brown under heating conditions at a high temperature of 900 to 1000 ° C. The degree of discoloration tends to increase as the amount of binder phase decreases. About the cause of discoloration, the result of having analyzed using X-ray diffraction is shown in FIG. According to the analysis results, it is understood that mainly the oxidation of WC is the dominant factor of this discoloration, since the precipitated phases generated in the discolored portion are WO 3 and NiWO 4 .

本発明の焼結体を回転工具として適用した場合、工具の損傷部位を修正して再利用する場合が考えられるが、これは、時に本発明の回転工具のコストを低減させるための重要な指針となる。ＷＯ３とＮｉＷＯ４の発生した部位は特性の変化が懸念されるため、工具の損傷部位に修正加工を施して再利用しようとした場合、発生したＷＯ３とＮｉＷＯ４を全て除去することが好ましい。また、ＷＯ３とＮｉＷＯ４の発生は、主に大気に長期間晒されうる回転工具の外周側面部で顕著に発生する。よって、回転工具の外周側面部に耐酸化性を付与し、ＷＯ３とＮｉＷＯ４の生成をできる限り抑制することが有効である。 When the sintered body of the present invention is applied as a rotary tool, it may be considered that the damaged part of the tool is corrected and reused, but this is sometimes an important guideline for reducing the cost of the rotary tool of the present invention. It becomes. Since there is a concern about changes in the properties of the portions where WO 3 and NiWO 4 are generated, it is preferable to remove all the generated WO 3 and NiWO 4 when attempting to carry out correction processing on the damaged portion of the tool for reuse. . In addition, the generation of WO 3 and NiWO 4 occurs notably on the outer peripheral side of the rotary tool which can be exposed to the atmosphere for a long time. Therefore, it is effective to provide oxidation resistance to the outer peripheral side surface portion of the rotary tool and to suppress the formation of WO 3 and NiWO 4 as much as possible.

そこで、この硬質相には、必要に応じて焼結体の酸化を抑制するための添加物であるＴｉＣ，ＴｉＮ，Ｔｉ（Ｃ，Ｎ），Ｃｒ３Ｃ２，ＴａＣ及びこれらとＷＣとの固溶体のうち何れか一つ或いは２つ以上を含有させることができる。そして、これらの添加物の添加によって、ＷＣの一部がＴｉＣ，ＴｉＮ，Ｔｉ（Ｃ，Ｎ），Ｃｒ３Ｃ２，ＴａＣに固溶するため、ＷＣ単独の場合と比較して焼結体中に存在するＷの存在比が少なくなる。その結果、酸化に寄与するＷの量が低減してＷＣの酸化が抑制される。 Therefore, if necessary, TiC, TiN, Ti (C, N), Cr 3 C 2 , TaC, and solid solutions of these with WC, which are additives for suppressing oxidation of the sintered body, are added to this hard phase. One or two or more of them can be contained. And, by the addition of these additives, a part of WC dissolves in TiC, TiN, Ti (C, N), Cr 3 C 2 , and TaC, so in the sintered body as compared with the case of WC alone. The abundance ratio of W present in As a result, the amount of W contributing to oxidation is reduced, and the oxidation of WC is suppressed.

表１には、酸化を抑制する前記添加物を含有する焼結体の例が試料Ｎｏ．Ｄ−９〜１２として示されている。これら試料Ｎｏ．Ｄ−９〜１２は、焼結体全体に対する金属結合相の体積比と金属結合相の組成とが試料Ｎｏ．Ｄ−２と同一であり、硬質相の添加物が相違する焼結体である。そこで、図１３に示す「条件２」によって試験を実施した試料Ｎｏ．Ｄ−２の工具先端部の外観と、図１４に示す同条件で試験を実施した試料Ｎｏ．Ｄ−１０の工具先端部の外観とを比較すると、ＴｉＣを添加した試料Ｎｏ．Ｄ−１０は、試料Ｎｏ．Ｄ−２よりもショルダ外周側面部７の変色が有意に少ないことが分かる。このことから、前記ＴｉＣ等の添加物には、焼結体の酸化を抑制する効果があると認められる。   Table 1 shows an example of a sintered body containing the additive that suppresses oxidation as Sample No. D-9 to 12 are shown. These sample Nos. D-9 to 12 show that the volume ratio of the metal bonding phase to the entire sintered body and the composition of the metal bonding phase are the same as in sample No. It is a sintered body which is the same as D-2 but differs in the additive of the hard phase. Therefore, for the sample No. 1 for which the test was performed under “condition 2” shown in FIG. The appearance of the tip of the tool D-2 and the sample No. 2 tested under the same conditions as shown in FIG. As compared with the appearance of the tool tip of D-10, the sample No. 1 to which TiC was added was added. D-10 is a sample No. It can be seen that the discoloration of the shoulder outer peripheral side portion 7 is significantly less than that of D-2. From this, it is recognized that the additive such as TiC has an effect of suppressing the oxidation of the sintered body.

また、本実施形態の焼結体から成る回転工具３は、上述のようにクリープ変形に対する耐性が高いため、その表面に耐酸化性被覆を施すことでも、該皮膜の効果を有効に発揮させて極めて高い酸化抑制効果を得ることができる。耐酸化性被覆は、例えば、Ｔｉ，Ｓｉ，Ａｌ，Ｃｒを主要な構成元素として含む窒化物、炭窒化物或いは酸窒化物の単層膜或いは多層膜によって構成することができる。このとき、被覆層の酸化開始温度は少なくとも９００℃以上であることが必要である。   In addition, since the rotary tool 3 made of the sintered body of the present embodiment has high resistance to creep deformation as described above, the effect of the coating can be effectively exhibited even by applying an oxidation resistant coating to the surface thereof. An extremely high oxidation inhibition effect can be obtained. The oxidation resistant coating can be formed of, for example, a single layer film or a multilayer film of nitride, carbonitride or oxynitride containing Ti, Si, Al and Cr as main constituent elements. At this time, the oxidation start temperature of the coating layer needs to be at least 900 ° C. or more.

この場合、回転工具３の表面、特にショルダ５の外周側面７の表面に耐酸化性被膜を施すと有効である。通常の摩擦攪拌工程の使用環境においては、このショルダ５の外周側面７が攪拌に直接寄与することはないため、耐酸化性が確保されている限り、該外周側面７の被覆層の厚みが損耗することなく維持される。更に、回転工具３の先端形状を修正した後も、ショルダ５の外周側面７は修正の必要が無いため、被覆層はそのまま維持される。つまり、ショルダ外周側面７の耐酸化性被覆層は、回転工具３の先端形状の修正に関わらず、恒久的に維持される。よって、摩擦攪拌工程に用いる回転工具として重要な課題である工具コストに対して、極めて高い削減効果を発揮する。   In this case, it is effective to apply an oxidation resistant coating to the surface of the rotary tool 3, in particular to the surface of the outer peripheral side surface 7 of the shoulder 5. Since the outer peripheral side surface 7 of the shoulder 5 does not directly contribute to the stirring in the normal use environment of the friction stirring process, the thickness of the coating layer of the outer peripheral side surface 7 is worn out as long as the oxidation resistance is ensured. It is maintained without doing. Furthermore, even after the tip shape of the rotary tool 3 is corrected, the outer circumferential side surface 7 of the shoulder 5 does not need to be corrected, so the covering layer is maintained as it is. That is, the oxidation resistant coating layer of the shoulder outer peripheral side surface 7 is permanently maintained regardless of the correction of the tip shape of the rotary tool 3. Thus, the tool cost can be extremely reduced with respect to the tool cost, which is an important issue as a rotary tool used in the friction stirring process.

以上の通り、本発明の実施例であるところの硬質焼結体及びそれを用いた回転工具は、高い破壊靭性を確保しながら、金属材料からなる被加工材が９００〜１０００℃に至る高温に加熱されながら加工される過酷な条件下においても、長期にわたり優れた耐久性を得ることができることが分かる。更に、その主な原料は一般的に用いられるＷＣ，Ｎｉ，Ａｌであり、上記特許文献３及び特許文献８等で使用される例えばＩｒのような高価な貴金属を主要成分として使用する必要性がなく、しかも一般的な粉末冶金法で製作することが可能であり、製造コストを抑制することもできる。   As described above, in the hard sintered body according to the embodiment of the present invention and the rotary tool using the same, the work material made of a metal material reaches a high temperature of 900 to 1000 ° C. while securing high fracture toughness. It can be seen that excellent durability can be obtained over a long period of time, even under severe conditions of processing while being heated. Furthermore, the main raw materials thereof are generally used WC, Ni, and Al, and it is necessary to use an expensive noble metal such as Ir, which is used in the above-mentioned Patent Document 3 and Patent Document 8 etc., as a main component. Also, it is possible to manufacture by a general powder metallurgy method, and the manufacturing cost can also be suppressed.

以上、本発明に係る硬質焼結体及びそれを用いた回転工具ついて説明してきたが、本発明は上記の実施形態に限定されることなく、特許請求の範囲の趣旨を逸脱しない範囲で様々な設計変更が可能であることは言うまでもない。   As described above, the hard sintered body according to the present invention and the rotary tool using the same have been described, but the present invention is not limited to the above-described embodiment, and various modifications are possible without departing from the scope of the claims. It goes without saying that design changes are possible.

１Ａ，１Ｂ 被加工材
２ 接合領域
３ 回転工具
４ プローブ
５ ショルダ
６ バックプレート
７ ショルダの外周側面
８ 回転工具の進行方向 1A, 1B Workpiece 2 Joint area 3 Rotary tool 4 Probe 5 Shoulder 6 Back plate 7 Outer peripheral side surface of shoulder 8 Direction of movement of rotary tool

Claims (5)

ＷＣを含む単一或いは複数の炭化物及び／又は炭窒化物で構成される硬質相と、遷移金属及び遷移金属を含む金属間化合物から成る金属結合相とを有する硬質焼結体であって、
前記金属結合相は、Ｎｉ及びＡｌを含み、前記焼結体全体に対して１５％以上かつ５５％以下の体積比を有しており、
更に、該金属結合相は、該金属結合相全体に対して４０％以上の体積比のＬ１２相（γ’相）と、１０％以下の体積比のＢ２相（β相）とで構成されている、
ことを特徴とする硬質焼結体。 A hard sintered body having a hard phase composed of one or more carbides and / or carbonitrides containing WC and a metal bonding phase composed of a transition metal and an intermetallic compound containing the transition metal,
The metal bonding phase contains Ni and Al, and has a volume ratio of 15% or more and 55% or less with respect to the entire sintered body,
Furthermore, the metal bonding phase is composed of an L1 2 phase (γ 'phase) having a volume ratio of 40% or more to a total of the metal bonding phase and a B2 phase (β phase) having a volume ratio of 10% or less. ing,
Hard sintered body characterized in that. 前記硬質相に、ＴｉＣ、ＴｉＮ、Ｔｉ（Ｃ，Ｎ）、Ｃｒ３Ｃ２、ＴａＣ、及びこれらとＷＣとの固溶体のうち何れか１つ或いは２つ以上を含む、請求項１に記載の硬質焼結体。 Said hard phase, TiC, TiN, Ti (C , N), Cr 3 C 2, TaC, and one or two or more any of the solid solutions of these and WC, the hard of claim 1 Sintered body. 請求項１又は請求項２に記載の硬質焼結体によって形成されている、
ことを特徴とする回転工具。 It is formed of the hard sintered body according to claim 1 or 2.
A rotary tool characterized by 請求項３に記載の回転工具の表面に、酸化開始温度９００℃以上の耐酸化性被覆が施されている回転工具。   A rotary tool having an oxidation resistant coating having an oxidation start temperature of 900 ° C. or higher on the surface of the rotary tool according to claim 3. 摩擦攪拌工程に用いられる、請求項３又は４に記載の回転工具。   The rotary tool according to claim 3 or 4, which is used in the friction stirring step.
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Publication number Priority date Publication date Assignee Title
JPS62105911A (en) * 1985-11-05 1987-05-16 Sumitomo Electric Ind Ltd Hard diamond mass and production thereof
US5271758A (en) * 1990-10-10 1993-12-21 Valenite Inc. Alumina ceramic-metal articles
US5905937A (en) * 1998-01-06 1999-05-18 Lockheed Martin Energy Research Corporation Method of making sintered ductile intermetallic-bonded ceramic composites
JP5079940B2 (en) * 2000-12-22 2012-11-21 日本特殊陶業株式会社 Tungsten carbide cemented carbide composite material sintered body
JP2006144089A (en) * 2004-11-22 2006-06-08 Tungaloy Corp Hard metal made of superfine particle
WO2007089882A2 (en) * 2006-01-31 2007-08-09 Genius Metal, Inc. High-performance friction stir welding tools
CN101323925A (en) * 2008-06-25 2008-12-17 华南理工大学 Tungsten carbide material with Ni3Al as cementing phase and preparation thereof
JP5633006B2 (en) * 2010-03-24 2014-12-03 公立大学法人大阪府立大学 Friction stir processing apparatus and friction stir processing method
CN101880810B (en) * 2010-07-08 2013-07-03 株洲特利亚硬质合金有限公司 Hard alloy containing nickel aluminide and boron copper base and preparation method thereof
CN102140603B (en) * 2011-03-24 2012-12-19 株洲硬质合金集团有限公司 Preparation method of hard alloy using nickel-aluminum intermetallic compound Ni3Al as bonding phase
CN102162058B (en) * 2011-04-07 2012-10-10 株洲硬质合金集团有限公司 Hard alloy taking nickel-aluminum intermetallic compound Ni3Al as binding phase and preparation method thereof
CN102154582B (en) * 2011-05-27 2013-01-30 株洲硬质合金集团有限公司 Preparation method of hard alloy taking nickel-aluminium intermetallic compound Ni3Al as binding phase
CN102560215A (en) * 2012-02-17 2012-07-11 中南大学 Ni3Al bonded ultra-fine grained tungsten carbide-based hard alloy and preparation method thereof
CN105907997B (en) * 2016-06-02 2018-06-29 华南理工大学 In-situ authigenic nanometer Al2O3Toughening WC-Ni3Al composite materials and preparation method thereof

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