JP6841441B2 - Manufacturing method of Mo-Si-B alloy, Mo-Si-B alloy and friction stir welding tool - Google Patents
Manufacturing method of Mo-Si-B alloy, Mo-Si-B alloy and friction stir welding tool Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims description 103
- 239000000956 alloy Substances 0.000 title claims description 103
- 229910008423 Si—B Inorganic materials 0.000 title claims description 85
- 238000003756 stirring Methods 0.000 title claims description 25
- 238000003466 welding Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 49
- 229910052719 titanium Inorganic materials 0.000 claims description 40
- 229910052726 zirconium Inorganic materials 0.000 claims description 39
- 229910052750 molybdenum Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 9
- 239000006104 solid solution Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910017305 Mo—Si Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 39
- 238000005266 casting Methods 0.000 description 36
- 238000000265 homogenisation Methods 0.000 description 34
- 238000012669 compression test Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910001069 Ti alloy Inorganic materials 0.000 description 7
- 229910000601 superalloy Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 229910001182 Mo alloy Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001739 density measurement Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007657 chevron notch test Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- 229910000691 Re alloy Inorganic materials 0.000 description 1
- 239000011184 SiC–SiC matrix composite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- -1 WC-Co Chemical class 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- 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
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
Description
本発明は、Ｍｏ−Ｓｉ−Ｂ系合金、Ｍｏ−Ｓｉ−Ｂ系合金の製造方法および摩擦撹拌接合用ツールに関する。 The present invention relates to a Mo-Si-B alloy, a method for producing a Mo-Si-B alloy, and a friction stir welding tool.
ジェットエンジンやガスタービンなどの熱機関を高効率で運転させるために、無冷却で使用可能な超高温材料が求められている。そのような材料として、従来から、高い融点および優れた高温強度を有するＭｏ−Ｓｉ−Ｂ合金が注目されているが、高密度であり、室温破壊靭性に劣るという問題があった。そこで、本発明者等は、Ｍｏ−Ｓｉ−Ｂ合金にＴｉＣを添加した合金を開発し、この合金が、Ｍｏ−Ｓｉ−Ｂ合金の優れた高温強度を維持したまま、Ｍｏ−Ｓｉ−Ｂ合金より低密度で、室温破壊靭性が高いことを確認している（例えば、特許文献１、２、非特許文献１乃至３参照）。 In order to operate heat engines such as jet engines and gas turbines with high efficiency, ultra-high temperature materials that can be used without cooling are required. As such a material, a Mo—Si—B alloy having a high melting point and excellent high temperature strength has been attracting attention, but there is a problem that it has a high density and is inferior in room temperature fracture toughness. Therefore, the present inventors have developed an alloy in which TiC is added to the Mo-Si-B alloy, and this alloy maintains the excellent high-temperature strength of the Mo-Si-B alloy while maintaining the Mo-Si-B alloy. It has been confirmed that the density is lower and the toughness at room temperature is high (see, for example, Patent Documents 1 and 2 and Non-Patent Documents 1 to 3).
また、本発明者等は、ＴｉＣと同様にＭｏと共晶反応することが知られているＺｒＣを、Ｍｏ−Ｓｉ−Ｂ合金に添加した合金も開発し、この合金も、ＴｉＣを添加した合金と同様に、Ｍｏ−Ｓｉ−Ｂ合金の優れた高温強度を維持したまま、Ｍｏ−Ｓｉ−Ｂ合金より低密度で、室温破壊靭性が高いことを確認している（例えば、非特許文献４参照）。 In addition, the present inventors have also developed an alloy in which ZrC, which is known to eutectic react with Mo like TiC, is added to a Mo—Si—B alloy, and this alloy is also an alloy to which TiC is added. Similarly, it has been confirmed that the Mo-Si-B alloy has a lower density and higher room temperature fracture toughness than the Mo-Si-B alloy while maintaining the excellent high-temperature strength (see, for example, Non-Patent Document 4). ).
なお、モリブデン合金ではないが、セラミックスである（Ｔｉ，Ｚｒ）Ｃが、ＴｉＣよりも著しく強度が高いことが、既に知られている（例えば、非特許文献５参照）。 It is already known that ceramics (Ti, Zr) C, which is not a molybdenum alloy, has significantly higher strength than TiC (see, for example, Non-Patent Document 5).
一方、従来の摩擦撹拌接合用のツールとして、ＳＫＤ６１などの工具鋼やＰＣＢＮツール、ＷＣ−Ｃｏなどの超硬合金、Ｗ−Ｒｅ合金およびＩｒ合金を用いたツール等が開発され、既に実用化されている。 On the other hand, as conventional tools for friction stir welding, tool steels such as SKD61, PCBN tools, cemented carbides such as WC-Co, tools using W-Re alloys and Ir alloys, etc. have been developed and have already been put into practical use. ing.
特許文献１等に記載のＴｉＣを添加したＭｏ−Ｓｉ−Ｂ系合金や、非特許文献４に記載のＺｒＣを添加したＭｏ−Ｓｉ−Ｂ系合金は、優れた高温強度を有しているが、さらに優れた高温強度特性を有する材料の開発が求められている。なお、非特許文献５には、ＴｉＣとＺｒＣとを含むセラミックスが記載されているが、ＴｉＣとＺｒＣとを含むモリブデン合金やＭｏ−Ｓｉ−Ｂ系合金については、記載も示唆もされていない。 Although the TiC-added Mo-Si-B alloy described in Patent Document 1 and the like and the ZrC-added Mo-Si-B alloy described in Non-Patent Document 4 have excellent high-temperature strength. Further, the development of a material having excellent high temperature strength characteristics is required. In Non-Patent Document 5, ceramics containing TiC and ZrC are described, but neither molybdenum alloys containing TiC and ZrC nor Mo—Si—B based alloys are described or suggested.
一方、インコネル（ＩＮＣＯＮＥＬ；登録商標）などのＮｉ基超合金やＴｉ合金は、高強度で高耐熱性を有していることから、それらを摩擦撹拌接合するのは困難であり、そのためのツールも限られている。特に、Ｎｉ基超合金については、ＰＣＢＮツール以外には適用例がない。このため、Ｎｉ基超合金やＴｉ合金用の摩擦撹拌接合用ツールの材料として、耐熱性、耐摩耗性、高靭性の新たな材料が求められている。 On the other hand, Ni-based superalloys such as INCONEL (registered trademark) and Ti alloys have high strength and high heat resistance, so it is difficult to perform friction stir welding between them, and tools for that purpose are also available. limited. In particular, there is no application example for Ni-based superalloys other than PCBN tools. Therefore, new materials with heat resistance, wear resistance, and high toughness are required as materials for friction stir welding tools for Ni-based superalloys and Ti alloys.
本発明は、このような課題に着目してなされたもので、より優れた高温強度特性を有するＭｏ−Ｓｉ−Ｂ系合金およびＭｏ−Ｓｉ−Ｂ系合金の製造方法、ならびに、Ｎｉ基超合金およびＴｉ合金に適用可能な摩擦撹拌接合用ツールを提供することを目的とする。 The present invention has been made by paying attention to such a problem, and a method for producing a Mo-Si-B-based alloy and a Mo-Si-B-based alloy having more excellent high-temperature strength characteristics, and a Ni-based superalloy. And to provide a friction stir welding tool applicable to Ti alloys.
本発明者等は、Ｍｏ−Ｓｉ−Ｂ合金に対して、ＴｉＣとＺｒＣとを同時に添加することにより、それぞれを単独で添加したものよりも劇的に高温強度が向上することを見出し、本発明に至った。 The present inventors have found that by adding TiC and ZrC to the Mo—Si—B alloy at the same time, the high temperature strength is dramatically improved as compared with the case where each of them is added alone. It came to.
すなわち、本発明に係るＭｏ−Ｓｉ−Ｂ系合金は、６０原子％以上７５原子％以下のＭｏと、１．７原子％以上６．７原子％以下のＳｉと、３．３原子％以上１３．３原子％以下のＢと、１．０原子％以上１４．０原子％以下のＴｉと、１．０原子％以上１４．０原子％以下のＺｒと、５．０原子％以上１５．０原子％以下のＣとを有し、残部が不可避不純物から成り、ＴｉＣとＺｒＣとの含有比が、９：１乃至１：９（原子比）であることを特徴とする。
That is, the Mo-Si-B based alloy according to the present invention includes Mo of 60 atomic% or more and 75 atomic% or less, Si of 1.7 atomic% or more and 6.7 atomic% or less, and 3.3 atomic% or more and 13 .B of 3 atomic% or less, Ti of 1.0 atomic% or more and 14.0 atomic% or less, Zr of 1.0 atomic% or more and 14.0 atomic% or less, 5.0 atomic% or more and 15.0 possess the atomic percent and C, the balance being unavoidable impurities, the content ratio of TiC and ZrC is 9: 1 to 1: characterized in that it is a 9 (atomic ratio).
本発明に係るＭｏ−Ｓｉ−Ｂ系合金は、Ｍｏ−Ｓｉ−Ｂ合金にＴｉＣまたはＺｒＣをそれぞれ単独で添加したものと比べて、優れた高温強度特性を有している。また、Ｍｏ−Ｓｉ−Ｂ合金と比べて、低密度で、室温破壊靭性が高い。 The Mo-Si-B alloy according to the present invention has excellent high-temperature strength characteristics as compared with the Mo-Si-B alloy to which TiC or ZrC is added alone. In addition, it has a lower density and higher room temperature fracture toughness than the Mo-Si-B alloy.
本発明に係るＭｏ−Ｓｉ−Ｂ系合金は、前記Ｔｉと前記Ｚｒとを合わせた組成比が、５原子％以上１５．０原子％以下であることが好ましい。また、Ｍｏ固溶体相、Ｍｏ５ＳｉＢ２、（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃの４相から成ることが好ましい。これらの場合、特に優れた高温強度特性を有している。
The Mo—Si—B alloy according to the present invention preferably has a composition ratio of Ti and Zr in combination of 5 atomic% or more and 15.0 atomic% or less . Also, Mo solid solution phase, Mo 5 SiB 2, (Ti , Zr, Mo) C, (Mo, Ti, Zr) is preferably comprised of 4 phases 2 C. In these cases, they have particularly excellent high-temperature strength characteristics.
本発明に係るＭｏ−Ｓｉ−Ｂ系合金の製造方法は、６０原子％以上７５原子％以下のＭｏと、１．７原子％以上６．７原子％以下のＳｉと、３．３原子％以上１３．３原子％以下のＢと、１．０原子％以上１４．０原子％以下のＴｉと、１．０原子％以上１４．０原子％以下のＺｒと、５．０原子％以上１５．０原子％以下のＣとを有し、残部が不可避不純物から成る原料を溶解して鋳造した後、１５００℃〜１９００℃で１時間〜１００時間の均質化熱処理を行うことにより、本発明に係るＭｏ−Ｓｉ−Ｂ系合金を製造することを特徴とする。
The method for producing a Mo—Si—B based alloy according to the present invention includes Mo of 60 atomic% or more and 75 atomic% or less, Si of 1.7 atomic% or more and 6.7 atomic% or less, and 3.3 atomic% or more. 13. B of 13.3 atomic% or less, Ti of 1.0 atomic% or more and 14.0 atomic% or less, Zr of 1.0 atomic% or more and 14.0 atomic% or less, and 5.0 atomic% or more 15. 0 possess the atomic percent and C, after the balance has been cast by dissolving formed Ru raw material from unavoidable impurities, by performing homogenization heat treatment for 1 to 100 hours at 1500 ° C. to 1900 ° C., the present invention It is characterized by producing such a Mo—Si—B based alloy.
本発明に係るＭｏ−Ｓｉ−Ｂ系合金の製造方法は、本発明に係るＭｏ−Ｓｉ−Ｂ系合金を製造することができる。本発明に係るＭｏ−Ｓｉ−Ｂ系合金の製造方法は、いわゆる鋳造法を利用するため、製造されるＭｏ−Ｓｉ−Ｂ系合金を大型化することができる。なお、ＴｉとＺｒとを合わせた組成比が、５原子％以上１５．０原子％以下であることが好ましい。均質化熱処理は、１７５０℃〜１８５０℃で２４時間〜３０時間行うことが特に好ましい。
The method for producing a Mo—Si—B alloy according to the present invention can produce a Mo—Si—B alloy according to the present invention. Since the method for producing a Mo—Si—B alloy according to the present invention utilizes a so-called casting method, the size of the produced Mo—Si—B alloy can be increased. The combined composition ratio of Ti and Zr is preferably 5 atomic% or more and 15.0 atomic% or less . Homogenization heat treatment is particularly preferably carried out 24 to 30 hours at 1750 ℃ ~1850 ℃.
本発明に係る摩擦撹拌接合用ツールは、本発明に係るＭｏ−Ｓｉ−Ｂ系合金から成ることを特徴とする。 The friction stir welding tool according to the present invention is characterized by being made of a Mo—Si—B based alloy according to the present invention.
本発明に係る摩擦撹拌接合用ツールは、高温強度特性に優れ、優れた耐熱性および耐摩耗性を有している。また、靭性も高いため、Ｎｉ基超合金およびＴｉ合金に適用することができる。本発明に係る摩擦撹拌接合用ツールは、粉末焼結体ではなく、鋳造法を利用して製造できるため、大型化が可能であり、巨大プラントでの利用も可能になる。また、本発明に係る摩擦撹拌接合用ツールは、ＷＣ−Ｃｏ超硬合金やＰＣＢＮツール等よりも安価に製造できるとともに、大量生産も可能である。 The friction stir welding tool according to the present invention has excellent high-temperature strength characteristics, and has excellent heat resistance and wear resistance. In addition, since it has high toughness, it can be applied to Ni-based superalloys and Ti alloys. Since the friction stir welding tool according to the present invention can be manufactured by using a casting method instead of a powder sintered body, it can be increased in size and can be used in a huge plant. Further, the friction stir welding tool according to the present invention can be manufactured at a lower cost than the WC-Co cemented carbide, the PCBN tool, and the like, and can also be mass-produced.
本発明に係る摩擦撹拌接合用ツールは、材料となる本発明に係るＭｏ−Ｓｉ−Ｂ系合金の切削加工が困難であるため、例えば、放電加工と切削加工と研削加工とを組み合わせることにより、所望の形状に加工することが好ましい。 Since it is difficult for the friction stir welding tool according to the present invention to cut the Mo—Si—B alloy according to the present invention as a material, for example, by combining electric discharge machining, cutting machining, and grinding machining, It is preferable to process it into a desired shape.
本発明に係るＭｏ−Ｓｉ−Ｂ系合金は、摩擦撹拌接合用ツールだけでなく、切削加工用工具や、Ｎｉ基超合金等の高耐熱性材料に対する熱間鍛造用の金型などにも使用することができる。また、SiC/SiC複合材料の代替材料として、次世代エンジンや火力発電用タービンの動・静翼にも使用することができる。 The Mo-Si-B alloy according to the present invention is used not only for friction stir welding tools, but also for cutting tools and dies for hot forging of highly heat-resistant materials such as Ni-based superalloys. can do. It can also be used as a substitute material for SiC / SiC composite materials for the dynamic and stationary blades of next-generation engines and turbines for thermal power generation.
本発明によれば、より優れた高温強度特性を有するＭｏ−Ｓｉ−Ｂ系合金およびＭｏ−Ｓｉ−Ｂ系合金の製造方法、ならびに、Ｎｉ基超合金およびＴｉ合金に適用可能な摩擦撹拌接合用ツールを提供することができる。 According to the present invention, a method for producing Mo-Si-B alloys and Mo-Si-B alloys having better high temperature strength characteristics, and for friction stir welding applicable to Ni-based superalloys and Ti alloys. Tools can be provided.
以下、実施例等に基づいて、本発明の実施の形態について説明する。
本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、６０原子％以上７５原子％以下のＭｏと、１．７原子％以上６．７原子％以下のＳｉと、３．３原子％以上１３．３原子％以下のＢと、１．０原子％以上１４．０原子％以下のＴｉと、１．０原子％以上１４．０原子％以下のＺｒと、５．０原子％以上１５．０原子％以下のＣとを有している。Hereinafter, embodiments of the present invention will be described based on examples and the like.
The Mo-Si—B based alloy according to the embodiment of the present invention contains Mo of 60 atomic% or more and 75 atomic% or less, Si of 1.7 atomic% or more and 6.7 atomic% or less, and 3.3 atomic% or more. 13. B of 13.3 atomic% or less, Ti of 1.0 atomic% or more and 14.0 atomic% or less, Zr of 1.0 atomic% or more and 14.0 atomic% or less, and 5.0 atomic% or more 15. It has C of 0 atomic% or less.
本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金の製造方法により好適に製造される。すなわち、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金の製造方法は、まず、６０原子％以上７５原子％以下のＭｏと、１．７原子％以上６．７原子％以下のＳｉと、３．３原子％以上１３．３原子％以下のＢと、１．０原子％以上１４．０原子％以下のＴｉと、１．０原子％以上１４．０原子％以下のＺｒと、５．０原子％以上１５．０原子％以下のＣとを有する原料を溶解して鋳造する。その後、１５００℃〜１９００℃で１時間〜１００時間の均質化熱処理を行う。これにより、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金を製造することができる。 The Mo—Si—B based alloy according to the embodiment of the present invention is suitably produced by the method for producing a Mo—Si—B based alloy according to the embodiment of the present invention. That is, in the method for producing the Mo—Si—B based alloy according to the embodiment of the present invention, first, Mo of 60 atomic% or more and 75 atomic% or less and Si of 1.7 atomic% or more and 6.7 atomic% or less are used. 3.3 B of 3.3 atomic% or more and 13.3 atomic% or less, Ti of 1.0 atomic% or more and 14.0 atomic% or less, Zr of 1.0 atomic% or more and 14.0 atomic% or less, and 5 A raw material having C of 0.0 atomic% or more and 15.0 atomic% or less is melted and cast. Then, a homogenizing heat treatment is performed at 1500 ° C. to 1900 ° C. for 1 hour to 100 hours. Thereby, the Mo—Si—B based alloy according to the embodiment of the present invention can be produced.
本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、Ｍｏ−Ｓｉ−Ｂ合金にＴｉＣまたはＺｒＣをそれぞれ単独で添加したものと比べて、優れた高温強度特性を有しており、優れた耐熱性および耐摩耗性を有している。また、Ｍｏ−Ｓｉ−Ｂ合金と比べて、低密度で、室温破壊靭性が高い。また、鋳造法を利用して製造されるため、大型化することができる。 The Mo-Si-B alloy according to the embodiment of the present invention has excellent high-temperature strength characteristics and is excellent as compared with the Mo-Si-B alloy to which TiC or ZrC is added alone. It has heat resistance and abrasion resistance. In addition, it has a lower density and higher room temperature fracture toughness than the Mo-Si-B alloy. Moreover, since it is manufactured by using a casting method, it can be increased in size.
本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金の製造方法により、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金を製造した。まず、６５原子％のＭｏと、５原子％のＳｉと、１０原子％のＢと、（１０−ｘ）原子％のＴｉと、ｘ原子％のＺｒと、１０原子％のＣとを有する原料（ここで、ｘ＝０〜１０）を、アルゴン雰囲気中で、アーク溶解により溶解して水冷銅鋳型に鋳造した。鋳塊の大きさは、φ１５ｍｍ、１２ｇのもの（以下、「小型鋳塊」と呼ぶ）およびφ５０ｍｍ、９０ｇのもの（以下、「大型鋳塊」と呼ぶ）の２種類とした。鋳造後、アルゴン雰囲気中で、１８００℃で２４時間の均質化熱処理を行った。 The Mo—Si—B alloy according to the embodiment of the present invention was produced by the method for producing a Mo—Si—B alloy according to the embodiment of the present invention. First, a raw material having 65 atomic% Mo, 5 atomic% Si, 10 atomic% B, (10-x) atomic% Ti, x atomic% Zr, and 10 atomic% C. (Here, x = 0 to 10) was melted by arc melting in an argon atmosphere and cast into a water-cooled copper mold. There were two types of ingots, one having a diameter of 15 mm and 12 g (hereinafter referred to as a “small ingot”) and the other having a diameter of 50 mm and 90 g (hereinafter referred to as a “large ingot”). After casting, homogenization heat treatment was performed at 1800 ° C. for 24 hours in an argon atmosphere.
ここでは、まず、６５Ｍｏ−５Ｓｉ−１０Ｂ−（１０−ｘ）Ｔｉ−ｘＺｒ−１０ＣのＭｏ−Ｓｉ−Ｂ系合金（ｘ＝１，２，５，７または８）のインゴットを製造した。なお、製造されたＭｏ−Ｓｉ−Ｂ系合金は、ＴｉとＺｒとを合わせた組成比がＣの組成比と等しく、ＴｉＣとＺｒＣとの含有比が、ｘ＝１のとき９：１、ｘ＝２のとき８：２、ｘ＝５のとき５：５、ｘ＝７のとき３：７、ｘ＝８のとき２：８となっている。 Here, first, an ingot of a Mo-Si-B alloy (x = 1,2,5,7 or 8) of 65Mo-5Si-10B- (10-x) Ti-xZr-10C was produced. In the produced Mo—Si—B alloy, the combined composition ratio of Ti and Zr is equal to the composition ratio of C, and the content ratio of TiC and ZrC is 9: 1, x when x = 1. When = 2, it is 8: 2, when x = 5, it is 5: 5, when x = 7, it is 3: 7, and when x = 8, it is 2: 8.
ＴｉＣ：ＺｒＣ＝９：１〜２：８（ｘ＝１，２，５，７，８）のときの、小型鋳塊の鋳造後の合金（As-cast alloys）の走査型電子顕微鏡（ＳＥＭ）写真を図１および図２に、均質化熱処理後の合金（Heat-treated alloys）のＳＥＭ写真を図３および図４に示す。また、ＴｉＣ：ＺｒＣ＝９：１〜２：８（ｘ＝１，２，５，７，８）のときの、小型鋳塊の鋳造後のＸ線回折（ＸＲＤ）パターンを図５に、均質化熱処理後のＸＲＤパターンを図６に示す。 Scanning electron microscope (SEM) of as-cast alloys after casting of small ingots when TiC: ZrC = 9: 1 to 2: 8 (x = 1,2,5,7,8) The photographs are shown in FIGS. 1 and 2, and the SEM photographs of the heat-treated alloys after the homogenization heat treatment are shown in FIGS. 3 and 4. Further, the X-ray diffraction (XRD) pattern after casting of the small ingot when TiC: ZrC = 9: 1 to 2: 8 (x = 1,2,5,7,8) is homogeneous in FIG. The XRD pattern after the chemical heat treatment is shown in FIG.
鋳造後は、図１および図５に示すように、ＴｉＣ：ＺｒＣ＝９：１および８：２のとき、インゴットの上部で、Ｍｏｓｓ［Ｍｏ固溶体相］および（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＴｉＣ］の２相の共晶、Ｍｏ５ＳｉＢ２［以下、「Ｔ２」とも記載する］、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ［主にＭｏ２Ｃ］の４相が存在していることが確認された。また、インゴットの下部で、Ｍｏｓｓ、Ｔ２および（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＴｉＣ］の３相の共晶、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ［主にＭｏ２Ｃ］の４相が存在していることが確認された。After casting, as shown in FIGS. 1 and 5, TiC: ZrC = 9: 1 and 8: When 2, at the top of the ingot, Mo ss [Mo solid solution phase] and (Ti, Zr, Mo) C [ There are four phases, mainly TiC] two-phase eutectic, Mo 5 SiB 2 [hereinafter also referred to as “T 2 ”], and (Mo, Ti, Zr) 2 C [mainly Mo 2 C]. It was confirmed that there was. Further, at the bottom of the ingot, Mo ss, T 2 and (Ti, Zr, Mo) C 3 phases of the eutectic of the mainly TiC], (Mo, Ti, Zr) 2 C [ mainly Mo 2 C] of It was confirmed that four phases existed.
また、図２および図５に示すように、ＴｉＣ：ＺｒＣ＝５：５〜２：８のとき、Ｍｏｓｓ［Ｍｏ固溶体相］および（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＺｒＣ］の２相の共晶、Ｍｏ５ＳｉＢ２［以下、「Ｔ２」とも記載する］、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ［主にＭｏ２Ｃ］の４相が存在していることが確認された。また、初晶が（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＺｒＣ］であることも確認された。また、インゴットの上部と下部で、ミクロ組織に顕著な違いは観察されなかった。ｘが大きくなるに従って、（Ｔｉ，Ｚｒ，Ｍｏ）Ｃの体積率が増加することが確認された。Further, as shown in FIGS. 2 and 5, TiC: ZrC = 5: 5~2: 8 When, Mo ss [Mo solid solution phase] and (Ti, Zr, Mo) C 2 phase [mainly ZrC] It was confirmed that there are four phases of eutectic, Mo 5 SiB 2 [hereinafter, also referred to as “T 2 ”] and (Mo, Ti, Zr) 2 C [mainly Mo 2 C]. It was also confirmed that the primary crystal was (Ti, Zr, Mo) C [mainly ZrC]. In addition, no significant difference was observed in the microstructure between the upper part and the lower part of the ingot. It was confirmed that the volume fraction of (Ti, Zr, Mo) C increased as x increased.
均質化熱処理後は、図３および図６に示すように、ＴｉＣ：ＺｒＣ＝９：１および８：２のとき、Ｍｏｓｓ、Ｍｏ５ＳｉＢ２、（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＴｉＣ］の３相から成ることが確認された。また、図４および図６に示すように、ＴｉＣ：ＺｒＣ＝５：５〜２：８のとき、Ｍｏｓｓ、Ｍｏ５ＳｉＢ２、（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ［主にＺｒＣ］、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ［主にＭｏ２Ｃ］の４相から成ることが確認された。また、ＴｉＣ／ＺｒＣが大きくなるに従って、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃの体積率が減少し、ｘ≦２で、全く認められなくなった。After the homogenizing heat treatment, as shown in FIGS. 3 and 6, TiC: ZrC = 9: 1 and 8: When 2, Mo ss, Mo 5 SiB 2, (Ti, Zr, Mo) C [ mainly TiC ] Was confirmed to consist of three phases. Further, as shown in FIGS. 4 and 6, TiC: ZrC = 5: 5~2: 8 When, Mo ss, Mo 5 SiB 2 , (Ti, Zr, Mo) C [ mainly ZrC], (Mo , Ti, Zr) It was confirmed that it consisted of 4 phases of 2 C [mainly Mo 2 C]. Further, according TiC / ZrC increases, (Mo, Ti, Zr) 2 C volume ratio is reduced, with x ≦ 2, was not recognized at all.
均質化熱処理後のＴｉＣ：ＺｒＣ＝９：１〜２：８（ｘ＝１，２，５，７，８）の小型鋳塊の各試料について、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ［以下、「Ｍｏ２Ｃ」とも記載する］の共析分解を観察した。その結果を図７に示す。図７に示すように、ＴｉＣ：ＺｒＣ＝５：５のときは、熱処理後に（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃの一部が分解しており、それよりもＴｉＣ／ＺｒＣが大きいときは、熱処理後に（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃが消失し、ＴｉＣ／ＺｒＣが小さいときは、熱処理後も（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃが存在していることが確認された。For each sample of a small ingot of TiC: ZrC = 9: 1 to 2: 8 (x = 1,2,5,7,8) after homogenization heat treatment, (Mo, Ti, Zr) 2 C [hereinafter, The eutectoid decomposition of [also referred to as "Mo 2 C"] was observed. The result is shown in FIG. As shown in FIG. 7, TiC: ZrC = 5: when the 5, after the heat treatment (Mo, Ti, Zr) 2 is partially decomposed and C, when it TiC / ZrC is greater than the heat treatment after (Mo, Ti, Zr) 2 C disappeared, when TiC / ZrC is small even after heat treatment (Mo, Ti, Zr) be 2 C is present was confirmed.
鋳造後および均質化熱処理後のＴｉＣ：ＺｒＣ＝９：１〜２：８（ｘ＝１，２，５，７，８）の小型鋳塊の各試料について、エネルギー分散型Ｘ線分光法（ＳＥＭ−ＥＤＸ）により、Ｍｏｓｓ、Ｍｏ５ＳｉＢ２、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ、初晶（primary）である（Ｔｉ，Ｚｒ，Ｍｏ）Ｃ、の各相の元素濃度を測定した。その測定結果を図８〜図１０に示す。なお、比較のため、図１０中には、ＴｉＣ：ＺｒＣ＝１０：０（ｘ＝０）および０：１０（ｘ＝１０）のときの大型鋳塊の測定結果も示す。Energy dispersive X-ray spectroscopy (SEM) for each sample of small ingots of TiC: ZrC = 9: 1-2: 8 (x = 1,2,5,7,8) after casting and homogenization heat treatment. the -EDX), Mo ss, Mo 5 SiB 2, were measured (Mo, Ti, Zr) 2 C, a primary crystal (primary) (Ti, Zr, Mo) C, each phase of the element concentration. The measurement results are shown in FIGS. 8 to 10. For comparison, FIG. 10 also shows the measurement results of the large ingot when TiC: ZrC = 10: 0 (x = 0) and 0:10 (x = 10).
図８〜図１０に示すように、鋳造後および均質化熱処理後の各試料とも、ＴｉＣ／ＺｒＣが小さくなるに従って、Ｍｏｓｓ、Ｍｏ５ＳｉＢ２、（Ｍｏ，Ｔｉ，Ｚｒ）２Ｃ中のＴｉの濃度が低下することが確認された。また、初晶（primary）の（Ｔｉ，Ｚｒ，Ｍｏ）Ｃは、ＴｉＣ／ＺｒＣが大きいとき（ｘ＝０，１，２のとき）、ＴｉおよびＭｏの濃度が高く、ＴｉＣ／ＺｒＣが小さいとき（ｘ＝５，７，８，１０のとき）、Ｚｒの濃度が高いことが確認された。As shown in FIGS. 8 to 10, in each sample after casting and after homogenization heat treatment, in accordance with TiC / ZrC is reduced, Mo ss, Mo 5 SiB 2 , (Mo, Ti, Zr) Ti in 2 C It was confirmed that the concentration of was reduced. Further, the primary (Ti, Zr, Mo) C has a high TiC / ZrC concentration (when x = 0, 1, 2), a high concentration of Ti and Mo, and a small TiC / ZrC. (When x = 5,7,8,10), it was confirmed that the concentration of Zr was high.
なお、小型鋳塊と大型鋳塊では、鋳造後および均質化熱処理後ともに、大型鋳塊の方がＭｏｓｓの結晶が大きくなっているのが確認されたが、各相の元素濃度やＸ線回折パターンには違いが認められなかった。Ｍｏｓｓの結晶の大きさが異なる原因としては、冷却速度の違いが考えられ、冷却速度を制御することにより、同じ合金組成でも機械的性質を変えることができるものと考えられる。In the small ingot and a large ingot, both after casting and after homogenization heat treatment, but the direction of a large ingot is large crystals of Mo ss is confirmed, each phase of the element concentration and X ray No difference was observed in the diffraction pattern. The cause of different sizes of Mo ss crystals, the difference in cooling rate is believed, by controlling the cooling rate is believed to be able to alter the mechanical properties of the same alloy composition.
鋳造後および均質化熱処理後のＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）の大型鋳塊の各試料、６５Ｍｏ−５Ｓｉ−１０Ｂ−５ＴｉＣ−５ＺｒＣについて、２ｍｍ×２ｍｍ×４ｍｍの大きさに切り出し、それぞれ１３００℃、１４００℃、１５００℃、１６００℃の真空中（＞１０−３Ｐａ）で、２．１×１０−４ｓ−１の条件で、高温圧縮試験を行った。また、比較のため、Ｍｏ−Ｓｉ−Ｂ合金に、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した２つの合金、６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＴｉＣ（ｘ＝０）および６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＺｒＣ（ｘ＝１０）の大型鋳塊についても、同じ条件で高温圧縮試験を行った。Each sample of TiC: ZrC = 5: 5 (x = 5) large ingot after casting and homogenization heat treatment, 65Mo-5Si-10B-5TiC-5ZrC, was cut into a size of 2 mm × 2 mm × 4 mm. A high temperature compression test was performed under the conditions of 2.1 × 10 -4 s -1 in vacuum (> 10 -3 Pa) at 1300 ° C., 1400 ° C., 1500 ° C., and 1600 ° C., respectively. Also, for comparison, two alloys, 65Mo-5Si-10B-10TiC (x = 0) and 65Mo-5Si-10B-10ZrC (x =), in which TiC and ZrC were added independently to the Mo-Si-B alloy, respectively. The large ingot of 10) was also subjected to a high temperature compression test under the same conditions.
各試料の試験結果を、図１１〜図１４に示す。また、図１３中には、これまでに調べられている他の合金の結果も合わせて示す。また、図１４には、温度条件が１４００℃のときの結果を示し、図１４（ｂ）には、過去に本発明者等が開発した２つのモリブデン合金、３８Ｍｏ−１７Ｓｉ−２５Ｔｉ−１０ＺｒＣおよび６２．２Ｍｏ−６．７Ｓｉ−１３．３Ｂ−８．９ＺｒＣの試験結果も示す。また、図１４（ｂ）に示す３つの試料について、高温圧縮試験後の状態を図１５（ａ）〜（ｃ）に示す。 The test results of each sample are shown in FIGS. 11 to 14. In addition, the results of other alloys investigated so far are also shown in FIG. Further, FIG. 14 shows the results when the temperature condition is 1400 ° C., and FIG. 14 (b) shows two molybdenum alloys developed by the present inventors in the past, 38Mo-17Si-25Ti-10ZrC and 62. The test results of .2Mo-6.7Si-13.3B-8.9ZrC are also shown. Further, the states of the three samples shown in FIG. 14 (b) after the high temperature compression test are shown in FIGS. 15 (a) to 15 (c).
図１１〜図１３、図１４（ａ）に示すように、鋳造後および均質化熱処理後の各試料とも、ＴｉＣとＺｒＣとを共添加した本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した合金と比べて、ピーク応力（Peak Stress）および０．２％耐力（0.2％ Proof Stress）が大きく、高温強度が高い傾向があることが確認された。特に、温度条件が１４００℃のときには、強度が１．３倍〜２倍程度になっており、顕著に上昇していることが確認された。また、図１３に示すように、他の合金と比べても、高温強度が高くなっていることが確認された。 As shown in FIGS. 11 to 13 and 14 (a), the Mo—Si—B alloy according to the embodiment of the present invention in which TiC and ZrC are co-added in each sample after casting and homogenization heat treatment. It was confirmed that the peak stress (Peak Stress) and 0.2% proof stress (0.2% Proof Stress) tended to be higher and the high temperature strength tended to be higher than the alloys to which TiC and ZrC were added alone. In particular, when the temperature condition was 1400 ° C., the intensity was about 1.3 to 2 times, and it was confirmed that the intensity increased remarkably. Further, as shown in FIG. 13, it was confirmed that the high temperature strength was higher than that of other alloys.
また、図１４（ｂ）に示すように、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、他のモリブデン合金と比べても、高温強度が高いことが確認された。また、図１４（ａ）および（ｂ）に示すように、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金は、他の合金と比べて、弾性限度を超えた後の流動応力の低下が小さいことも確認された。また、図１５に示すように、高温圧縮試験後、他のモリブデン合金の試料では、巨視的なき裂が明確に認められるのに対して、本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金の試料ではき裂が認められず、良好な破壊靭性が確認された。 Further, as shown in FIG. 14B, it was confirmed that the Mo—Si—B based alloy according to the embodiment of the present invention has higher high temperature strength than other molybdenum alloys. Further, as shown in FIGS. 14 (a) and 14 (b), the Mo—Si—B based alloy according to the embodiment of the present invention has a lower flow stress after exceeding the elastic limit than other alloys. Was also confirmed to be small. Further, as shown in FIG. 15, after the high temperature compression test, macroscopic cracks are clearly observed in the samples of other molybdenum alloys, whereas the Mo—Si—B alloy according to the embodiment of the present invention is observed. No cracks were observed in the sample, and good fracture toughness was confirmed.
次に、均質化熱処理後のＴｉＣ：ＺｒＣ＝９：１〜１：９（ｘ＝１，２，３，４，５，６，７，８，９）の小型鋳塊の各試料についても、同じ条件で高温圧縮試験を行った。また、比較のため、Ｍｏ−Ｓｉ−Ｂ合金に、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した２つの合金、６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＴｉＣ（ｘ＝０）および６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＺｒＣ（ｘ＝１０）の小型鋳塊についても、同じ条件で高温圧縮試験を行った。ただし、試験温度は、１４００℃のみとした。 Next, for each sample of TiC: ZrC = 9: 1 to 1: 9 (x = 1,2,3,4,5,6,7,8,9) after homogenization heat treatment, A high temperature compression test was performed under the same conditions. Also, for comparison, two alloys, 65Mo-5Si-10B-10TiC (x = 0) and 65Mo-5Si-10B-10ZrC (x =), in which TiC and ZrC were added independently to the Mo-Si-B alloy, respectively. The small ingot of 10) was also subjected to a high temperature compression test under the same conditions. However, the test temperature was only 1400 ° C.
各試料の試験結果を、同じ条件で実施した小型鋳塊の結果と合わせて、図１６および図１７に示す。図１６および図１７に示すように、ＴｉＣ：ＺｒＣ＝９：１〜１：９（ｘ＝１，２，３，４，５，６，７，８，９）のとき、ピーク応力（Peak Stress）は、ＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）で最大となることが確認された。また、０．２％耐力（0.2％ Proof Stress）は、ＴｉＣ：ＺｒＣ＝４：６（ｘ＝６）で最大となることが確認された。また、ＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）のとき、ピーク応力は、小型鋳塊の方が大型鋳塊よりも大きく、０．２％耐力は、小型鋳塊も大型鋳塊もほぼ同じ値であることが確認された。小型鋳塊と大型鋳塊のピーク応力の違いは、冷却速度の違いによるものと考えられる。 The test results of each sample are shown in FIGS. 16 and 17 together with the results of the small ingots carried out under the same conditions. As shown in FIGS. 16 and 17, when TiC: ZrC = 9: 1 to 1: 9 (x = 1,2,3,4,5,6,7,8,9), peak stress (Peak Stress) ) Was confirmed to be maximum at TiC: ZrC = 5: 5 (x = 5). It was also confirmed that the 0.2% proof stress (0.2% Proof Stress) was maximized at TiC: ZrC = 4: 6 (x = 6). Further, when TiC: ZrC = 5: 5 (x = 5), the peak stress of the small ingot is larger than that of the large ingot, and the 0.2% proof stress is almost the same for both the small ingot and the large ingot. It was confirmed that the values were the same. The difference in peak stress between the small ingot and the large ingot is considered to be due to the difference in the cooling rate.
鋳造後および均質化熱処理後のＴｉＣ：ＺｒＣ＝９：１〜１：９（ｘ＝１，２，３，４，５，６，７，８，９）の小型鋳塊の各試料、ならびに、鋳造後および均質化熱処理後のＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）の大型鋳塊の各試料について、室温でビッカース（Ｖｉｃｋｅｒｓ）硬さの測定を行った。測定時の荷重は、１ｋｇｆとした。また、鋳造後および均質化熱処理後のＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）の大型鋳塊の各試料について、４点曲げ試験および密度測定を行った。４点曲げ試験は、各試料を１．５×２×２５ｍｍの大きさに成形し、シェブロンノッチ法で行った。また、クロスヘッドの移動速度は、０．３μｍ／ｓとした。 Samples of small ingots of TiC: ZrC = 9: 1 to 1: 9 (x = 1,2,3,4,5,6,7,8,9) after casting and homogenization heat treatment, and Vickers hardness was measured at room temperature for each sample of a large ingot with TiC: ZrC = 5: 5 (x = 5) after casting and after homogenization heat treatment. The load at the time of measurement was 1 kgf. In addition, a four-point bending test and density measurement were performed on each sample of a large ingot of TiC: ZrC = 5: 5 (x = 5) after casting and homogenization heat treatment. The 4-point bending test was performed by molding each sample into a size of 1.5 × 2 × 25 mm and using the chevron notch method. The moving speed of the crosshead was 0.3 μm / s.
室温におけるビッカース硬さの測定結果を、図１８に示す。なお、比較のため、Ｍｏ−Ｓｉ−Ｂ合金に、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した、均質化熱処理後の２つの合金、６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＴｉＣ（ｘ＝０）および６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＺｒＣ（ｘ＝１０）の小型鋳塊および大型鋳塊についての測定結果も示す。図１８に示すように、熱処理により若干硬さが低下するものの、鋳造後ではＨＶ８５０以上、均質化熱処理後でもＨＶ８００以上であり、非常に硬いことが確認された。また、鋳造後および均質化熱処理後ともに、小型鋳塊の方が大型鋳塊よりも硬いことが確認された。この硬さの違いは、冷却速度の違いによるものと考えられる。 The measurement result of Vickers hardness at room temperature is shown in FIG. For comparison, two alloys after homogenization heat treatment, 65Mo-5Si-10B-10TiC (x = 0) and 65Mo-5Si-, in which TiC and ZrC were added independently to the Mo-Si-B alloy, respectively. The measurement results for small ingots and large ingots of 10B-10ZrC (x = 10) are also shown. As shown in FIG. 18, although the hardness was slightly reduced by the heat treatment, it was HV850 or more after casting and HV800 or more even after the homogenization heat treatment, and it was confirmed that the hardness was very hard. It was also confirmed that the small ingot was harder than the large ingot both after casting and after homogenization heat treatment. This difference in hardness is considered to be due to the difference in cooling rate.
室温で得られた４点曲げ試験による荷重−変位曲線を図１９に、電磁超音波共鳴法で求められたヤング率やポアソン比を表１に、これらのデータを使いＩｒｗｉｎの相似則に従って求められた室温破壊靭性値を図２０に示す。また、密度の測定結果を、図２１に示す。なお、比較のため、Ｍｏ−Ｓｉ−Ｂ合金に、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した、均質化熱処理後の２つの合金、６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＴｉＣ（１０ＴｉＣ；ｘ＝０）および６５Ｍｏ−５Ｓｉ−１０Ｂ−１０ＺｒＣ（１０ＺｒＣ；ｘ＝１０）についての測定結果も示す。密度測定の１０ＴｉＣの試料のみ小型鋳塊であり、他の比較試料は大型鋳塊である。 The load-displacement curve obtained by the 4-point bending test obtained at room temperature is shown in FIG. 19, and the Young's modulus and Poisson's ratio obtained by the electromagnetic ultrasonic resonance method are shown in Table 1, and these data are used to obtain the load-displacement curve according to Irwin's similarity law. The room temperature breaking toughness value is shown in FIG. The density measurement result is shown in FIG. For comparison, two alloys after homogenization heat treatment, 65Mo-5Si-10B-10TiC (10TiC; x = 0) and 65Mo-, in which TiC and ZrC were added independently to the Mo-Si-B alloy, respectively. The measurement results for 5Si-10B-10ZrC (10ZrC; x = 10) are also shown. Only the 10TiC sample for density measurement is a small ingot, and the other comparative samples are large ingots.
図２０に示すように、鋳造後および均質化熱処理後の各試料とも、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した合金と比べて、室温破壊靭性値がやや低下しているものの、十分に大きい室温破壊靭性値を有していることが確認された。また、図２１に示すように、鋳造後および均質化熱処理後の各試料とも、ＴｉＣおよびＺｒＣをそれぞれ単独で添加した合金とほぼ同じ密度であり、Ｍｏ−Ｓｉ−Ｂ合金より低密度であることが確認された。 As shown in FIG. 20, the room temperature fracture toughness values of each of the samples after casting and after homogenization heat treatment are slightly lower than those of the alloy to which TiC and ZrC are added alone, but they are sufficiently large at room temperature fracture. It was confirmed that it had a toughness value. Further, as shown in FIG. 21, each sample after casting and after homogenization heat treatment has substantially the same density as the alloy to which TiC and ZrC are added alone, and has a lower density than the Mo-Si-B alloy. Was confirmed.
ＴｉＣ：ＺｒＣ＝５：５（ｘ＝５）の本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金、６５Ｍｏ−５Ｓｉ−１０Ｂ−５ＴｉＣ−５ＺｒＣに対し、放電加工と切削加工と研削加工とを組み合わせて加工し、図２２に示す摩擦撹拌接合用ツールを作製した。図２２に示すように、作製した摩擦撹拌接合用ツールは、ツール全体が本発明の実施の形態のＭｏ−Ｓｉ−Ｂ系合金で形成されている。図２２に示す摩擦撹拌接合用ツールは、ピン部の先端の直径が約３．５ｍｍ、ピン部の円形台座の直径が約１５ｍｍである。 Electric discharge machining, cutting and grinding are performed on 65Mo-5Si-10B-5TiC-5ZrC, a Mo-Si-B alloy according to the embodiment of the present invention of TiC: ZrC = 5: 5 (x = 5). The tools were combined and machined to produce the friction stir welding tool shown in FIG. As shown in FIG. 22, in the produced friction stir welding tool, the entire tool is formed of the Mo—Si—B based alloy according to the embodiment of the present invention. In the friction stir welding tool shown in FIG. 22, the diameter of the tip of the pin portion is about 3.5 mm, and the diameter of the circular pedestal of the pin portion is about 15 mm.
図２２に示す摩擦撹拌接合用ツールを用いて、インコネル（ＩＮＣＯＮＥＬ；登録商標）６００、６４チタン合金（Ｔｉ−６Ａｌ−４Ｖ）およびＳＵＳ３０４の摩擦撹拌を行った。摩擦撹拌後の各被加工材の状態を、図２３（ａ）〜（ｃ）に示す。図２３（ａ）〜（ｃ）に示すように、各被加工材に対して問題なく摩擦撹拌できており、摩擦撹拌接合可能であることが確認された。
Friction stir welding of INCONEL (registered trademark) 600, 64 titanium alloy (Ti-6Al-4V) and SUS304 was performed using the friction stir welding tool shown in FIG. The states of each work material after friction stir welding are shown in FIGS. 23 (a) to 23 (c). As shown in FIGS. 23 (a) to 23 (c), it was confirmed that friction stir welding was possible for each work material without any problem, and that friction stir welding was possible.
Claims (5)
A friction stir welding tool comprising the Mo—Si—B alloy according to any one of claims 1 to 3.
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