JP6392179B2 - Method for deoxidizing Ti-Al alloy - Google Patents
Method for deoxidizing Ti-Al alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims description 127
- 229910045601 alloy Inorganic materials 0.000 title claims description 116
- 229910004349 Ti-Al Inorganic materials 0.000 title claims description 101
- 229910004692 Ti—Al Inorganic materials 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 60
- 239000001301 oxygen Substances 0.000 claims description 84
- 229910052760 oxygen Inorganic materials 0.000 claims description 84
- 238000002844 melting Methods 0.000 claims description 79
- 230000008018 melting Effects 0.000 claims description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 78
- 230000004907 flux Effects 0.000 claims description 57
- 239000010936 titanium Substances 0.000 claims description 48
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 43
- 229910052719 titanium Inorganic materials 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 15
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 230000006698 induction Effects 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 238000011978 dissolution method Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910010038 TiAl Inorganic materials 0.000 description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/003—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals by induction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/20—Arc remelting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、チタン材料およびアルミニウム材料よりなる、酸素を合計で０．１質量％以上含有する合金材料を用いて作製したＴｉ−Ａｌ系合金から酸素を除去するＴｉ−Ａｌ系合金の脱酸方法に関するものである。 The present invention relates to a Ti-Al alloy deoxidation method for removing oxygen from a Ti-Al alloy produced using an alloy material comprising a titanium material and an aluminum material and containing 0.1 mass% or more of oxygen in total. It is about.
近年、航空機や自動車向けの金属素材としてＴｉ−Ａｌ系合金の需要が高まりつつある。このような活性金属のチタンを主成分とするＴｉ−Ａｌ系合金等のチタン合金を製造する際には、溶解中の酸素による汚染を防ぐ必要があり、従来から真空アーク溶解法（ＶＡＲ）、電子ビーム溶解法（ＥＢ）、プラズマアーク溶解法（ＰＡＭ）、真空誘導溶解法（ＶＩＭ）、水冷銅式誘導溶解法（ＣＣＩＭ）などの溶解法が採用されてきた。 In recent years, the demand for Ti-Al alloys as metal materials for aircraft and automobiles is increasing. When producing a titanium alloy such as a Ti-Al alloy containing titanium as an active metal as a main component, it is necessary to prevent contamination by oxygen during melting. Conventionally, a vacuum arc melting method (VAR), Melting methods such as electron beam melting (EB), plasma arc melting (PAM), vacuum induction melting (VIM), and water-cooled copper induction melting (CCIM) have been adopted.
上記した溶解法の中でも、ＶＡＲ、ＥＢ、ＶＩＭといった溶解法は真空雰囲気下で合金の溶解を行う溶解法であり、Ｔｉ−Ａｌ系合金の溶解に、このような溶解法を採用した場合、合金元素であるＡｌだけではなく、Ｔｉについても溶解中に揮発してしまいロスを生じることになる。つまり、工業プロセスにおいて、Ｔｉ−Ａｌ系合金を目標の組成に制御することは極めて困難であり、その結果、製造コストの増加を招くことにもつながっているのが現状である。 Among the above melting methods, melting methods such as VAR, EB, and VIM are melting methods in which an alloy is melted in a vacuum atmosphere. When such a melting method is used for melting a Ti-Al alloy, an alloy is used. Not only Al, which is an element, but also Ti volatilizes during melting, causing loss. That is, in an industrial process, it is extremely difficult to control the Ti—Al-based alloy to a target composition, and as a result, the manufacturing cost is increased.
また、酸素含有量が少ないＴｉ−Ａｌ系合金を溶製するためには、酸素含有量が少ない高品位なチタン材料を用いてＴｉ−Ａｌ系合金を製造することが有効であるが、高品位なチタン材料は、高価格であり、特に近年は高騰する傾向にあるため、高品位なチタン材料より酸素含有量は多いが、廉価なスポンジチタン、スクラップ原料、ルチル鉱石（ＴｉＯ２）などの比較的低品位なチタン材料を用いてＴｉ−Ａｌ合金を製造したいというニーズが日々高まっている。 In order to melt a Ti-Al alloy having a low oxygen content, it is effective to produce a Ti-Al alloy using a high-grade titanium material having a low oxygen content. Titanium materials are expensive and have a tendency to soar in recent years, so the oxygen content is higher than high-grade titanium materials, but cheap sponge titanium, scrap raw materials, rutile ore (TiO 2 ), etc. There is a growing need to manufacture Ti-Al alloys using low-grade titanium materials.
Ｔｉは活性金属であり、溶解する雰囲気中に存在する不純物、特に酸素との結合力が極めて強いため、溶解中に外部から取り込まれる酸素を低減し、いかに汚染を防ぐかという対策が従来からなされていた。しかし、一度Ｔｉ中に固溶した酸素を除去することは容易ではなく、その取り組み自体が少ないのが現状であるが、先行技術としては以下に示すような提案がある。 Since Ti is an active metal and has a very strong binding force with impurities, especially oxygen, present in the melting atmosphere, measures have been conventionally taken to reduce oxygen taken from the outside during melting and prevent contamination. It was. However, it is not easy to remove oxygen once dissolved in Ti, and the efforts themselves are few at present, but there are proposals as shown below as prior art.
特許文献１には、低酸素Ｔｉ−Ａｌ系合金の製造方法および低酸素Ｔｉ−Ａｌ系合金に関する発明が開示されているが、その段落［００１３］には、「１×１０−２Ｔｏｒｒよりも高い真空雰囲気下において強制的にＡｌを除去すると、これに伴って溶湯中の酸素量も減少するのであり、最終目標組成のＡｌ含有量よりもＡｌを多く含有する組成の溶湯から強制的にＡｌを除去することにより、最終目標組成のＴｉ−Ａｌ系合金を製造することができると同時に酸素を２００ｐｐｍ以下に低減させることができる。」と記載されている。 Patent Document 1 discloses a method for producing a low-oxygen Ti—Al-based alloy and an invention related to a low-oxygen Ti—Al-based alloy. In paragraph [0013], “1 × 10 −2 Torr than When Al is forcibly removed in a high vacuum atmosphere, the amount of oxygen in the molten metal is reduced accordingly, and the Al is forced from the molten metal having a composition containing more Al than the Al content of the final target composition. By removing this, it is possible to produce a Ti—Al-based alloy having the final target composition and simultaneously reduce oxygen to 200 ppm or less. ”
すなわち、特許文献１に記載された低酸素Ｔｉ−Ａｌ系合金の製造方法は、１．３３Ｐａ（１×１０−２Ｔｏｒｒ）よりも低い圧力の高真空雰囲気下において低酸素Ｔｉ−Ａｌ系合金を製造する方法であり、このような高真空雰囲気における溶解では、合金元素であるＡｌだけではなく、Ｔｉについても揮発ロスを生じることになり、低酸素Ｔｉ−Ａｌ系合金の製造方法としては有効な方法であるということができるが、余分にＴｉおよびＡｌを添加する必要があり、製造コストの増加が懸念される。 That is, the method for producing a low oxygen Ti—Al based alloy described in Patent Document 1 uses a low oxygen Ti—Al based alloy in a high vacuum atmosphere at a pressure lower than 1.33 Pa (1 × 10 −2 Torr). Such melting in a high vacuum atmosphere causes volatilization loss not only for the alloy element Al, but also for Ti, and is effective as a method for producing a low oxygen Ti—Al alloy. Although this method can be said to be a method, it is necessary to add extra Ti and Al, and there is a concern about an increase in manufacturing cost.
また、特許文献２には、低酸素Ｔｉ−Ａｌ系合金およびその製造方法に関する発明が開示されており、その段落［００１０］には、「本発明は、上記の問題点を解決するためになされたもので、Ｔｉ−Ａｌを主成分とする合金系の溶製において、Ｃａで脱酸し、過剰のＣａを蒸発除去することおよび無汚染均一溶解によって、高純度の低酸素Ｔｉ−Ａｌ系合金およびその製造方法を提供することを目的とする。」と記載されている。 Patent Document 2 discloses an invention relating to a low-oxygen Ti—Al-based alloy and a method for producing the same, and paragraph [0010] describes that “the present invention is made in order to solve the above problems. In high-purity low-oxygen Ti-Al alloy by deoxidizing with Ca, evaporating and removing excess Ca and non-contaminating homogeneous dissolution And an object thereof is to provide a manufacturing method thereof ”.
この方法は、低酸素Ｔｉ−Ａｌ系合金を製造するために有効な方法であるということができるが、金属Ｃａ添加溶解並びに金属Ｃａ除去、そして均質化のための溶解という複数の工程を経る方法であり、また、金属Ｃａはチタン中に固溶するため、残留Ｃａの完全な除去が困難な方法でもあり、製造コストおよび製造時間の増加、除去しきれなかった残留ＣａによるＴｉ−Ａｌ系合金の汚染、各種特性の変化が懸念される方法である。 Although this method can be said to be an effective method for producing a low-oxygen Ti—Al-based alloy, it is a method that undergoes a plurality of steps of melting and adding metal Ca, removing metal Ca, and melting for homogenization. In addition, since the metal Ca is dissolved in titanium, it is difficult to completely remove the residual Ca. Therefore, the manufacturing cost and the manufacturing time are increased, and the Ti—Al based alloy due to the residual Ca that cannot be completely removed. This is a method of concern for contamination and changes in various properties.
特許文献３には、ＴｉＡｌ基合金の鋳塊製造方法に関する発明が開示されており、その段落［００１７］には酸素含有量を鋳塊の全ての領域で低減できることが記載されている。また、その請求項１には、「Ｔｉ原料の酸素含有量を８００ｐｐｍ以下、Ａｌ原料の酸素含有量を１００ｐｐｍ以下とすると共に、他の合金成分がＣｒ、Ｖ、Ｎｂの場合はそれらの酸素含有量を２０００ｐｐｍ以下、他の合金成分がＭｎの場合はその酸素含有量を３０００ｐｐｍ以下とすることを特徴とするＴｉＡｌ基合金の鋳塊製造方法。」と記載されている。 Patent Document 3 discloses an invention related to a method for producing a TiAl-based alloy ingot, and paragraph [0017] describes that the oxygen content can be reduced in all regions of the ingot. In addition, the claim 1 states that “the oxygen content of the Ti raw material is 800 ppm or less, the oxygen content of the Al raw material is 100 ppm or less, and when the other alloy components are Cr, V, Nb, the oxygen content thereof. The method for producing an ingot of a TiAl-based alloy characterized in that when the amount is 2000 ppm or less and the other alloy component is Mn, its oxygen content is 3000 ppm or less.
このように、特許文献３に記載されたＴｉＡｌ基合金の鋳塊製造方法は、鋳塊の酸素含有量を低減できる有効な方法であるといえるが、この方法は、酸素含有量が低い高品位な材料を用いて、酸素含有量の低いＴｉＡｌ基合金を得ようとする方法であり、酸素含有量が比較的高い低品位なＴｉ材料を用いた方法ではない。また、実施例にはＡｌの含有量が３０質量％と低いＴｉＡｌ合金しか記載されていない。 Thus, it can be said that the ingot manufacturing method of the TiAl-based alloy described in Patent Document 3 is an effective method that can reduce the oxygen content of the ingot, but this method is a high-quality low oxygen content. This method is to obtain a TiAl-based alloy having a low oxygen content using a simple material, and is not a method using a low-grade Ti material having a relatively high oxygen content. In the examples, only a TiAl alloy having a low Al content of 30% by mass is described.
また、特許文献４には、チタン−アルミニウム合金鋳造物の鋳造方法に関する発明が開示されており、原料としてのスポンジチタンを溶融し、その溶融チタン中に、原料としてのアルミニウムを添加して、所定量のチタンおよびアルミニウムを含有するチタンーアルミニウム合金を調整することが記載されており、その請求項２および段落［００２０］には、そのスポンジチタンの酸素含有量が３５０ｐｐｍ以下であること、また、実施例にはスポンジチタンの酸素含有量が０．０３ｗｔ％であることが記載されている。 Patent Document 4 discloses an invention relating to a casting method of a titanium-aluminum alloy casting, in which sponge titanium as a raw material is melted, and aluminum as a raw material is added to the molten titanium. It is described that a titanium-aluminum alloy containing a fixed amount of titanium and aluminum is prepared, and in claim 2 and paragraph [0020], the oxygen content of the sponge titanium is 350 ppm or less, and In the examples, it is described that the oxygen content of titanium sponge is 0.03 wt%.
このように、特許文献４に記載されたチタン−アルミニウム合金鋳造物の鋳造方法では、原料として酸素含有量が３５０ｐｐｍ以下（０．０３５質量％以下に相当）の高品位なスポンジチタンが用いられており、酸素含有量が低い高品位な材料を用いて、酸素含有量の低いチタン−アルミニウム合金鋳造物を得ようとする方法であり、酸素含有量が比較的高い低品位なチタン材料を用いた方法ではない。また、実施例にはＡｌの含有量が３４質量％と低いチタン−アルミニウム合金鋳造物しか記載されていない。 Thus, in the casting method of the titanium-aluminum alloy casting described in Patent Document 4, high-grade sponge titanium having an oxygen content of 350 ppm or less (corresponding to 0.035 mass% or less) is used as a raw material. In this method, a high-grade material with a low oxygen content is used to obtain a cast titanium-aluminum alloy with a low oxygen content, and a low-grade titanium material with a relatively high oxygen content is used. Not a way. Moreover, only the titanium-aluminum alloy casting whose content of Al is as low as 34 mass% is described in the Example.
本発明は、上記従来の問題を解決せんとしてなされたもので、酸素含有量が高い低品位なチタン材料を用いて、目標の組成でしかも酸素含有量が少ないＴｉ−Ａｌ系合金を、高真空雰囲気としなくても容易に製造することができるＴｉ−Ａｌ系合金の脱酸方法を提供することを課題とするものである。 The present invention has been made as a solution to the above-described conventional problems, and uses a low-grade titanium material having a high oxygen content, and a Ti-Al alloy having a target composition and a low oxygen content can be used in a high vacuum. It is an object of the present invention to provide a Ti—Al-based alloy deoxidation method that can be easily manufactured without an atmosphere.
本発明のＴｉ−Ａｌ系合金の脱酸方法は、チタン材料およびアルミニウム材料よりなる、酸素を合計で０．１質量％以上含有する合金材料を用いて作製した、Ａｌを４０質量％以上含有するＴｉ−Ａｌ系合金を、１．３３Ｐａ以上の雰囲気下で、水冷銅容器を用いた溶解法によって溶解し、保持することにより、前記Ｔｉ−Ａｌ系合金の酸素含有量を低下させることを特徴とする。 The Ti-Al alloy deoxidation method of the present invention contains 40 mass% or more of Al produced by using an alloy material made of a titanium material and an aluminum material and containing 0.1 mass% or more of oxygen in total. The Ti-Al-based alloy is melted by a melting method using a water-cooled copper container in an atmosphere of 1.33 Pa or more and held, thereby reducing the oxygen content of the Ti-Al-based alloy. To do.
また、前記Ｔｉ−Ａｌ合金を溶解する前或いは溶解中に、酸化カルシウムにフッ化カルシウムを３５〜９５質量％配合したＣａＯ−ＣａＦ２フラックスを添加することが好ましい。 Moreover, it is preferable to add CaO—CaF 2 flux in which 35 to 95% by mass of calcium fluoride is mixed with calcium oxide before or during melting of the Ti—Al alloy.
また、前記水冷銅容器を用いた溶解法は、アーク溶解法、プラズマアーク溶解法、誘導溶解法の何れかであることが好ましい。 The melting method using the water-cooled copper container is preferably any one of an arc melting method, a plasma arc melting method, and an induction melting method.
本発明のＴｉ−Ａｌ系合金の脱酸方法によると、酸素含有量が０．１質量％以上と高い低品位で廉価なチタン材料を用いて、ＡｌおよびＴｉの揮発ロスが少なく（実質的に低下させることなく）、目標の組成で、しかも酸素含有量が少ないＴｉ−Ａｌ系合金を、高真空雰囲気としなくても容易に製造することができる。 According to the Ti—Al-based alloy deoxidation method of the present invention, a low-quality and inexpensive titanium material having an oxygen content of 0.1 mass% or more is used, and the volatilization loss of Al and Ti is small (substantially A Ti—Al alloy having a target composition and a low oxygen content can be easily manufactured without a high vacuum atmosphere (without lowering).
尚、本発明のＴｉ−Ａｌ系合金の脱酸方法によって得られるＡｌ含有量が４０質量％以上で且つ酸素含有量が少ないＴｉ−Ａｌ系合金を、低酸素チタンで希釈すれば、Ａｌ含有量が４０質量％未満で且つ酸素含有量が少ないＴｉ−Ａｌ系合金を、比較的容易に且つ廉価に製造することが可能である。 In addition, if the Ti content obtained by the deoxidation method of the Ti—Al based alloy of the present invention is 40% by mass or more and the Ti—Al based alloy having a small oxygen content is diluted with low oxygen titanium, the Al content is obtained. Is less than 40% by mass and a Ti-Al alloy having a low oxygen content can be produced relatively easily and inexpensively.
本発明者らは、低品位なスポンジチタン、スクラップ原料や、ルチル鉱石（ＴｉＯ２）などの酸素を多く含有する低品位なチタン材料を用いて、ＡｌおよびＴｉの揮発ロスが少なく（実質的に低下させることなく）、目標の組成で、しかも酸素含有量が少ないＴｉ−Ａｌ系合金を、高真空雰囲気としなくても容易に製造できる方法を見出すため、鋭意検討を行った。 The inventors use low-grade titanium materials containing a large amount of oxygen such as low-grade sponge titanium, scrap raw materials, and rutile ore (TiO 2 ), so that the volatilization loss of Al and Ti is small (substantially) In order to find a method that can easily produce a Ti—Al alloy having a target composition and a low oxygen content without a high vacuum atmosphere (without reducing it), intensive studies were conducted.
Ｔｉ−Ａｌ系合金中に固溶する最大酸素量は、Ｘ．Ｌ．Ｌｉ，Ｒ．Ｈｉｌｌｅｌ，Ｆ．Ｔｅｙｓｓａｎｄｉｅｒ，Ｓ．Ｋ．Ｃｈｏｉ，ａｎｄ Ｆ．Ｊ．Ｊ．Ｖａｎ．Ｌｏｏ，Ａｃｔａ Ｍｅｔａｌｌ．Ｍａｔｅｒ．，４０｛１１｝３１４７−３１５７（１９９２）に示されたＴｉ−Ａｌ−Ｏの３元系状態図によると、図５に示す破線のような関係になると想定される。この事実から、本発明者らは高濃度のＡｌを含有するＴｉ−Ａｌ系合金は固溶酸素濃度が低くなるということに着目した。その結果、低品位なチタン材料を用いて作製したＴｉ−Ａｌ系合金であっても、Ａｌを４０質量％以上含有するＴｉ−Ａｌ系合金であれば、高真空雰囲気下でなくとも水冷銅容器を用いた溶解で脱酸反応が進行し、また、ＡｌやＴｉの揮発ロスが少なく（実質的に低下させることなく）、目標の組成の低酸素Ｔｉ−Ａｌ系合金を容易に製造できることを見出し、本発明を完成させるに至った。 The maximum amount of oxygen dissolved in the Ti—Al alloy is X. L. Li, R.R. Hillel, F.M. Teyssandier, S .; K. Choi, and F.C. J. et al. J. et al. Van. Loo, Acta Metall. Mater. , 40 {11} 3147-3157 (1992), it is assumed that the relation shown by the broken line in FIG. 5 is obtained. From this fact, the present inventors paid attention to the fact that a Ti—Al-based alloy containing a high concentration of Al has a low solid solution oxygen concentration. As a result, even if it is a Ti-Al alloy produced using a low-grade titanium material, if it is a Ti-Al alloy containing 40 mass% or more of Al, it is a water-cooled copper container even in a high vacuum atmosphere. It has been found that deoxidation reaction proceeds by dissolution using bismuth, and that low loss of Al and Ti volatilization is small (substantially without reduction), and that a low-oxygen Ti—Al alloy having a target composition can be easily produced. The present invention has been completed.
また、更に検討を進めた結果、Ｔｉ−Ａｌ系合金を溶解する前或いは溶解中に、チタン中で固溶しない特定の成分組成のＣａＯ−ＣａＦ２フラックスを脱酸反応促進剤として添加することで、その脱酸反応はより確実に進行することを併せて見出した。尚、Ｔｉ−Ａｌ系合金へのＣａＯ−ＣａＦ２フラックス添加よる脱酸反応は、Ｔｉ−Ａｌ系合金の脱酸生成物であるＡｌ２Ｏ３が、添加したＣａＯ−ＣａＦ２フラックスに固溶することで発現する現象であり、そのＣａＯ−ＣａＦ２フラックスの融点は、Ｔｉ−Ａｌ系合金の溶解温度と推定される概ね１８００Ｋ以下であることが必要である。 Further, as a result of further study, by adding a CaO—CaF 2 flux having a specific component composition not dissolved in titanium as a deoxidation reaction accelerator before or during melting of the Ti—Al alloy. The present inventors also found that the deoxidation reaction proceeds more reliably. In addition, in the deoxidation reaction by adding CaO-CaF 2 flux to Ti-Al alloy, Al 2 O 3 which is a deoxidation product of Ti-Al alloy is dissolved in the added CaO-CaF 2 flux. The melting point of the CaO—CaF 2 flux needs to be approximately 1800 K or less, which is estimated as the melting temperature of the Ti—Al alloy.
以下、本発明を実施形態に基づいて更に詳細に説明する。 Hereinafter, the present invention will be described in more detail based on embodiments.
本発明のＴｉ−Ａｌ系合金の脱酸方法は、チタン材料およびアルミニウム材料よりなる、酸素を合計で０．１質量％以上含有する合金材料を用いて作製した、Ａｌを４０質量％以上含有するＴｉ−Ａｌ系合金を、１．３３Ｐａ以上の雰囲気下で、水冷銅容器を用いたアーク溶解法、プラズマアーク溶解法、誘導溶解法などの溶解法によって溶解し、保持することにより、前記Ｔｉ−Ａｌ合金の酸素含有量を低下させる方法であって、前記チタン材料としては、低品位なスポンジチタン、スクラップ原料や、ルチル鉱石（ＴｉＯ２）などを用いる。 The Ti-Al alloy deoxidation method of the present invention contains 40 mass% or more of Al produced by using an alloy material made of a titanium material and an aluminum material and containing 0.1 mass% or more of oxygen in total. By dissolving and holding the Ti—Al-based alloy by an arc melting method using a water-cooled copper container, a plasma arc melting method, an induction melting method, or the like in an atmosphere of 1.33 Pa or more, the Ti— In this method, the oxygen content of the Al alloy is reduced, and as the titanium material, low-grade sponge titanium, scrap raw material, rutile ore (TiO 2 ), or the like is used.
Ｔｉ−Ａｌ系合金の作製に、低品位なスポンジチタン、スクラップ原料や、ルチル鉱石（ＴｉＯ２）などの酸素含有量が多いチタン材料を用いる理由は、これらチタン材料が廉価であり調達し易いからである。これらチタン材料およびアルミニウム材料よりなる合金材料の酸素の合計含有量を０．１質量％以上としたのは、合金材料中の酸素の合計含有量が０．１質量％未満であれば、酸素の含有量は僅かであり脱酸自体が必要ないからである。尚、本発明では、酸素の含有量の上限は規定しないが、前記合金材料に実際に含有される酸素の合計含有量の上限は、２５．０質量％程度であると考えられる。 The reason for using titanium materials with a high oxygen content such as low-grade sponge titanium, scrap raw materials, and rutile ore (TiO 2 ) for the production of Ti-Al alloys is because these titanium materials are inexpensive and easy to procure. It is. The total oxygen content of the alloy material composed of these titanium material and aluminum material is set to 0.1 mass% or more if the total oxygen content in the alloy material is less than 0.1 mass%. This is because the content is small and deoxidation itself is not necessary. In the present invention, the upper limit of the oxygen content is not specified, but the upper limit of the total content of oxygen actually contained in the alloy material is considered to be about 25.0% by mass.
また、前記チタン材料およびアルミニウム材料なる合金材料を用いて作製したＴｉ−Ａｌ系合金のＡｌ含有量を４０質量％以上とした理由は、Ｔｉ−Ａｌ系合金中のＡｌ含有量が４０質量％以上であれば、高真空雰囲気下ではなくて、１．３３Ｐａ以上の雰囲気下であっても、水冷銅容器を用いたアーク溶解法、プラズマアーク溶解法、誘導溶解法などの溶解法によって、Ｔｉ−Ａｌ系合金の脱酸反応が進行するからである。この脱酸反応はＡｌ含有量が高いＴｉ−Ａｌ系合金において固溶酸素濃度が低下し、過飽和な酸素がＡｌと結合し、Ａｌ２Ｏ３を形成することで発現する現象である。すなわち、Ａｌ２Ｏ３の形態で酸素がＴｉ−Ａｌ系合金中から排出される。Ｔｉ−Ａｌ系合金のＡｌ含有量が４０質量％以上であれば、Ｔｉ−Ａｌ系合金が溶解する概ね１８００Ｋ以上の温度で脱酸反応が進行する。 Moreover, the reason why the Al content of the Ti-Al alloy produced using the titanium material and the alloy material made of the aluminum material is 40 mass% or more is that the Al content in the Ti-Al alloy is 40 mass% or more Then, even in an atmosphere of 1.33 Pa or higher, not in a high vacuum atmosphere, by a melting method such as an arc melting method using a water-cooled copper container, a plasma arc melting method, an induction melting method, Ti- This is because the deoxidation reaction of the Al-based alloy proceeds. This deoxidation reaction is a phenomenon that occurs when the concentration of solid solution oxygen in a Ti-Al alloy having a high Al content decreases and supersaturated oxygen combines with Al to form Al 2 O 3 . That is, oxygen is discharged from the Ti—Al alloy in the form of Al 2 O 3 . When the Al content of the Ti—Al alloy is 40% by mass or more, the deoxidation reaction proceeds at a temperature of approximately 1800 K or more at which the Ti—Al alloy is dissolved.
尚、本発明では、チタン材料およびアルミニウム材料なる合金材料を用いて作製したＴｉ−Ａｌ系合金のＡｌ含有量の上限は特に規定していないが、好ましい上限は７０質量％、より好ましくは６０質量％、更に好ましくは５０質量％である。Ｔｉ−Ａｌ系合金はＡｌ以外の他の合金元素や酸素などの不純物も含有するので、合金元素であるＡｌの含有量が多くなり過ぎるとＴｉの割合が少なくなりＴｉ−Ａｌ系合金ということができなくなる。また、１．３３Ｐａ以上の雰囲気下とし、その上限は規定しなかったが、実際の上限は５．３３×１０５Ｐａ程度であると想定できる。 In the present invention, the upper limit of the Al content of a Ti-Al alloy produced using an alloy material such as a titanium material and an aluminum material is not particularly defined, but the preferable upper limit is 70% by mass, more preferably 60% by mass. %, More preferably 50% by mass. Ti-Al alloys contain other alloy elements other than Al and impurities such as oxygen. Therefore, if the content of Al, which is an alloy element, increases too much, the proportion of Ti decreases and it is called a Ti-Al alloy. become unable. Moreover, although it was set as the atmosphere of 1.33 Pa or more and the upper limit was not prescribed | regulated, it can be assumed that an actual upper limit is about 5.33 * 10 < 5 > Pa.
また、Ｔｉ−Ａｌ系合金の脱酸を行うにあたり、Ｔｉ−Ａｌ合金を溶解する前或いは溶解中に、脱酸反応促進剤としてフラックスを添加することで、脱酸反応をより確実に進行させることができる。このＴｉ−Ａｌ系合金に脱酸反応促進剤として添加するフラックスはＴｉ−Ａｌ系合金の溶解温度より低い融点の低融点フラックスである必要があり、本発明では低融点フラックスの中でも、性能、品質、コストの観点から最も好ましいと思われるＣａＯ−ＣａＦ２フラックスを採用することとした。 In addition, when deoxidizing a Ti-Al alloy, the deoxidation reaction can be advanced more reliably by adding a flux as a deoxidation reaction accelerator before or during the dissolution of the Ti-Al alloy. Can do. The flux added as a deoxidation reaction accelerator to the Ti-Al alloy must be a low melting point flux having a melting point lower than the melting temperature of the Ti-Al alloy. The CaO—CaF 2 flux, which seems to be most preferable from the viewpoint of cost, was adopted.
酸素含有量が少ないＴｉ−Ａｌ系合金を製造するにあたり、このＣａＯ−ＣａＦ２フラックスをＴｉ−Ａｌ系合金に添加することで脱酸反応がより促進されるが、前記したように、ＣａＯ−ＣａＦ２フラックスの融点が、Ｔｉ−Ａｌ系合金の溶解温度である約１８００Ｋ以下でなければ脱酸反応は促進されない。フラックス添加によって脱酸反応が促進される理由は、脱酸反応によって生成されたＡｌ２Ｏ３がフラックス中に吸収されることで、Ａｌ２Ｏ３の活量が低下し、それに伴って酸素濃度が低下するためである。 In producing a Ti—Al based alloy having a low oxygen content, the deoxidation reaction is further promoted by adding this CaO—CaF 2 flux to the Ti—Al based alloy, but as described above, the CaO—CaF The deoxidation reaction is not accelerated unless the melting point of the two fluxes is about 1800 K or less, which is the melting temperature of the Ti—Al alloy. The reason why the deoxidation reaction is promoted by the addition of the flux is that Al 2 O 3 produced by the deoxidation reaction is absorbed in the flux, so that the activity of Al 2 O 3 is reduced, and the oxygen concentration is accordingly reduced. This is because of a decrease.
尚、Ａｌ脱酸反応は以下の式（１）で示すことができ、反応定数は式（２）で示すことができる。本脱酸反応が発現するＡｌ／Ａｌ２Ｏ３平衡状態下において、式（２）のＫは一定となるが、脱酸反応によるａＡｌ変化はほとんどないため、以下の式（２）中のａＡｌ２Ｏ３が低下すると（フラックス中に吸収されると限りなくゼロに近付く）、それに伴って式（２）中のＰＯ２（含有酸素濃度）も低下する。
２Ａｌ（ｉｎＡｌ）＋３／２Ｏ２（ｉｎＴｉ−Ａｌ）＝Ａｌ２Ｏ３・・・式（１）
Ｋ＝ａＡｌ２Ｏ３／（ａＡｌ２・ＰＯ２ ３／２）・・・式（２）
The Al deoxidation reaction can be represented by the following formula (1), and the reaction constant can be represented by the formula (2). Under the Al / Al 2 O 3 equilibrium state in which the present deoxidation reaction is expressed, K in the formula (2) is constant, but since there is almost no change in aAl due to the deoxidation reaction, aAl in the following formula (2) When 2 O 3 decreases (approaching zero as much as it is absorbed in the flux), PO 2 (containing oxygen concentration) in formula (2) also decreases accordingly.
2Al (inAl) + 3 / 2O 2 (inTi-Al) = Al 2 O 3 ··· Equation (1)
K = aAl 2 O 3 / (aAl 2 · PO 2 3/2 ) Formula (2)
ＣａＯ−ＣａＦ２フラックスのフッ化カルシウムの配合量が３５質量％未満である場合は、ＣａＯ−ＣａＦ２フラックスの融点が１８００Ｋを超えてしまい、ＣａＯ−ＣａＦ２フラックス添加による脱酸反応の促進作用を得ることができない。一方、フッ化カルシウムの配合量が９５質量％を超えると、フッ素による汚染が発生する。よって、本発明では、酸化カルシウムにフッ化カルシウムを３５〜９５質量％配合したＣａＯ−ＣａＦ２フラックスを添加する。このＣａＯ−ＣａＦ２フラックスのフッ化カルシウムのより好ましい配合量は、６０〜９０質量％である。尚、ＣａＯ−ＣａＦ２フラックスの添加量は、Ｔｉ−Ａｌ系合金の質量に対して、５〜２０％の質量とすることが好ましい。 When the blending amount of calcium fluoride in the CaO-CaF 2 flux is less than 35% by mass, the melting point of the CaO-CaF 2 flux exceeds 1800K, and the deoxidation reaction promoting action by adding the CaO-CaF 2 flux is promoted. Can't get. On the other hand, when the blending amount of calcium fluoride exceeds 95% by mass, contamination with fluorine occurs. Therefore, in the present invention, the addition of CaO-CaF 2 flux was blended 35 to 95 wt% of calcium fluoride to calcium oxide. The more preferable amount of calcium fluoride in the CaO—CaF 2 flux is 60 to 90% by mass. The addition amount of CaO-CaF 2 flux, relative to the weight of Ti-Al alloy, it is preferable that 5 to 20 percent by weight.
尚、本発明のＴｉ−Ａｌ系合金の脱酸方法は、Ｔｉ−Ａｌ系合金のＡｌやＴｉの揮発ロスが少なく（実質的に低下させることなく）、酸素含有量を低下させる方法であると説明したが、実質的に許容することができるＡｌやＴｉの含有量の低下率は、５．０％以下である。つまり、実質的にとは５．０％以下のことを示す。 In addition, the deoxidation method of the Ti—Al based alloy of the present invention is a method of reducing the oxygen content with little (without substantially reducing) the volatilization loss of Al or Ti of the Ti—Al based alloy. Although demonstrated, the fall rate of content of Al and Ti which can be accept | permitted substantially is 5.0% or less. That is, substantially means 5.0% or less.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、本発明の趣旨に適合し得る範囲で適宜変更を加えて実施することも可能であり、それらは何れも本発明の技術的範囲に含まれる。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and the present invention is implemented with appropriate modifications within a range that can meet the gist of the present invention. These are all included in the technical scope of the present invention.
（Ｔｉ−Ａｌ系合金中のＡｌ含有量と溶解後の酸素含有量の関係）
・プラズマアーク溶解法、フラックス添加無
チタン材料およびアルミニウム材料からなる合金材料を用いて作製した、酸素含有量が０．８質量％のＴｉ−Ａｌ系合金の脱酸を、水冷銅容器を用いた１００ｋＷプラズマアーク炉で溶解し、その後保持することにより実施した。Ｔｉ−Ａｌ系合金のＡｌ含有量が溶解による脱酸反応に与える影響を調べるため、Ａｌ含有量が１０質量％、２０質量％、３０質量％、４０質量％、５０質量％、６０質量％のＴｉ−Ａｌ系合金をそれぞれ用いて作製したサンプルを準備した。尚、各サンプルは１００ｇとし、プラズマガスはＡｒのみを使用、溶解中の圧力は１．２０×１０５Ｐａとした。１００ｋＷプラズマアーク炉を用いて溶解、保持を行った後のＴｉ−Ａｌ系合金中のＡｌ濃度（Ａｌ含有量）と溶解後の酸素濃度（酸素含有量）の関係を図１に示す。
(Relation between Al content in Ti-Al alloy and oxygen content after dissolution)
・ Plasma arc melting method, flux addition-free Deoxidation of Ti-Al alloy with oxygen content of 0.8% by mass using an alloy material made of titanium material and aluminum material using a water-cooled copper container It was carried out by melting in a 100 kW plasma arc furnace and holding it thereafter. In order to investigate the influence of the Al content of the Ti—Al based alloy on the deoxidation reaction due to dissolution, the Al content is 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, and 60% by mass. Samples prepared using Ti-Al alloys were prepared. Each sample was 100 g, only Ar was used as the plasma gas, and the pressure during dissolution was 1.20 × 10 5 Pa. FIG. 1 shows the relationship between the Al concentration (Al content) in the Ti-Al alloy after melting and holding using a 100 kW plasma arc furnace and the oxygen concentration (oxygen content) after melting.
図１によると、Ａｌ含有量が１０〜３０質量％までのＴｉ−Ａｌ系合金の溶解後の酸素含有量は０．８質量％前後で変化がないが、Ａｌ含有量が４０質量％以上のＴｉ−Ａｌ系合金では溶解後に酸素含有量が低下していることがわかる。この結果から、Ｔｉ−Ａｌ系合金のＡｌ含有量が４０質量％以上になると溶解により脱酸反応が進行することがわかる。 According to FIG. 1, the oxygen content after melting of the Ti-Al alloy having an Al content of 10 to 30% by mass does not change around 0.8% by mass, but the Al content is 40% by mass or more. It can be seen that in the Ti-Al alloy, the oxygen content decreases after melting. From this result, it can be seen that when the Al content of the Ti-Al alloy is 40% by mass or more, the deoxidation reaction proceeds by dissolution.
・プラズマアーク溶解法、フラックス添加有
また、前記試験で溶解後に酸素含有量が低下した、Ａｌ含有量が、３０質量％、４０質量％、６０質量％のＴｉ−Ａｌ系合金について、ＣａＯ−ＣａＦ２フラックス添加による脱酸反応の促進の状況を調べるため、ＣａＯ−ＣａＦ２フラックスの添加以外は、フラックスを添加しない時と全く同じ条件として、プラズマアーク溶解によるＴｉ−Ａｌ合金の脱酸を実施した。尚、ＣａＯ−ＣａＦ２フラックス中のフッ化カルシウムの配合量は８０質量％、ＣａＯ−ＣａＦ２フラックスの添加量は５ｇとした。結果を図１に示す。
・ Plasma arc melting method, with flux addition In addition, with regard to Ti—Al based alloys whose oxygen content decreased after melting in the above test and whose Al content was 30% by mass, 40% by mass, and 60% by mass, CaO—CaF In order to investigate the progress of the deoxidation reaction by addition of 2 flux, Ti-Al alloy was deoxidized by plasma arc melting under exactly the same conditions as when no flux was added except for the addition of CaO-CaF 2 flux. . Incidentally, the amount of calcium fluoride CaO-CaF 2 in the flux 80 wt%, the added amount of CaO-CaF 2 flux was 5g. The results are shown in FIG.
図１によると、ＣａＯ−ＣａＦ２フラックスを添加した場合は、Ａｌ含有量が、４０質量％、６０質量％の何れの場合においても、ＣａＯ−ＣａＦ２フラックスを添加しない場合に比べ、更に脱酸が促進されていることが分かる。因みに、溶解後のＴｉ−Ａｌ合金中の酸素含有量（質量比、以下酸素含有量は全て質量比で示す。）は、Ａｌ含有量が４０質量％の場合で、ＣａＯ−ＣａＦ２フラックスを添加しない時が５４００ｐｐｍ、ＣａＯ−ＣａＦ２フラックスを添加した時が２４００ｐｐｍであり、また、Ａｌ含有量が６０質量％の場合で、ＣａＯ−ＣａＦ２フラックスを添加しない時が２８０ｐｐｍ、ＣａＯ−ＣａＦ２フラックスを添加した時が２２０ｐｐｍである。 According to FIG. 1, the case of adding CaO-CaF 2 flux, Al content of 40 mass%, in either case of 60 mass percent, compared to the case without the addition of CaO-CaF 2 flux, further deoxidation It can be seen that is promoted. Incidentally, the oxygen content in the Ti-Al alloy after melting (mass ratio, hereinafter all oxygen contents are shown by mass ratio) is the case where the Al content is 40% by mass and the CaO-CaF 2 flux is added. not when the 5400Ppm, is 2400ppm is upon addition of CaO-CaF 2 flux, and in case the Al content is 60 wt%, when no addition of CaO-CaF 2 flux 280 ppm, a CaO-CaF 2 flux When added, it is 220 ppm.
・チタン材料として酸化チタン材料を用いた場合
また、別途、酸化チタン材料およびアルミニウム材料からなる合金材料を用いて作製した、酸素含有量が１６．３質量％のＴｉ−Ａｌ系合金の脱酸を、水冷銅容器を用いた１００ｋＷプラズマアーク炉で溶解し、その後保持することにより実施した。このとき、Ｔｉ−Ａｌ系合金のＡｌ含有量は６０質量％とし、ＣａＯ−ＣａＦ２フラックスを添加する場合と添加しない場合の両方を実施した。尚、プラズマガスはＡｒのみを使用、溶解中の圧力は１．２０×１０５Ｐａとし、ＣａＯ−ＣａＦ２フラックス中のフッ化カルシウムの配合量は８０質量％、ＣａＯ−ＣａＦ２フラックスの添加量は５ｇとした。
When a titanium oxide material is used as the titanium material In addition, deoxidation of a Ti-Al alloy having an oxygen content of 16.3% by mass produced separately using an alloy material composed of a titanium oxide material and an aluminum material is performed. It was carried out by melting in a 100 kW plasma arc furnace using a water-cooled copper container and holding it thereafter. At this time, the Al content of the Ti—Al-based alloy was set to 60% by mass, and both the case where the CaO—CaF 2 flux was added and the case where it was not added were performed. The plasma gas uses only Ar, the pressure during dissolution is 1.20 × 10 5 Pa, the compounding amount of calcium fluoride in the CaO—CaF 2 flux is 80% by mass, and the addition amount of the CaO—CaF 2 flux Was 5 g.
溶解、保持を行った後のＴｉ−Ａｌ系合金中の酸素含有量はＣａＯ−ＣａＦ２フラックスを添加しない場合で５４０ｐｐｍ程度であり、酸化チタンを原料に用いて酸素含有量が１０質量％を超えるような材料であっても、脱酸効果がかなり発揮されていた。ＣａＯ−ＣａＦ２フラックスを添加する場合では、Ｔｉ−Ａｌ系合金中の酸素含有量は３３０ｐｐｍ程度であり、フラックスを添加することで、一層脱酸効果が発揮されることが確認できた。 The oxygen content in the Ti-Al alloy after melting and holding is about 540 ppm when no CaO-CaF 2 flux is added, and the oxygen content exceeds 10 mass% using titanium oxide as a raw material. Even with such a material, the deoxidation effect was considerably exhibited. In the case of adding the CaO—CaF 2 flux, the oxygen content in the Ti—Al based alloy is about 330 ppm, and it was confirmed that the deoxidation effect was further exhibited by adding the flux.
・誘導溶解法、フラックス添加無
また、プラズマアーク溶解法に変えて、水冷銅容器を用いた誘導溶解法を採用し、前記プラズマアーク溶解法と同様に酸素含有量が０．８質量％のＴｉ−Ａｌ系合金からの脱酸試験を実施した。Ｔｉ−Ａｌ系合金のＡｌ含有量が脱酸反応に与える影響を調べるため、Ａｌ含有量が３７質量％、３９質量％、５１質量％のＴｉ−Ａｌ系合金をそれぞれ溶製した。尚、各溶解において、溶解量は２０ｋｇとし、溶解チャンバー内雰囲気はＡｒ、溶解中の圧力は７．０×１０４Ｐａとした。誘導溶解炉を用いて溶解、保持を行った後のＴｉ−Ａｌ系合金中のＡｌ濃度（Ａｌ含有量）と酸素濃度（酸素含有量）の関係を、プラズマアーク溶解法を用いた場合のデータと併せて図１に示す。
・ Inductive melting method, no flux added In addition, instead of the plasma arc melting method, an induction melting method using a water-cooled copper container is adopted, and Ti having an oxygen content of 0.8 mass% is used as in the plasma arc melting method. -A deoxidation test from an Al-based alloy was performed. In order to investigate the influence of the Al content of the Ti—Al based alloy on the deoxidation reaction, Ti—Al based alloys having an Al content of 37 mass%, 39 mass%, and 51 mass% were respectively melted. In each dissolution, the dissolution amount was 20 kg, the atmosphere in the dissolution chamber was Ar, and the pressure during dissolution was 7.0 × 10 4 Pa. Data on the relationship between Al concentration (Al content) and oxygen concentration (oxygen content) in Ti-Al alloys after melting and holding using an induction melting furnace when using plasma arc melting method Together with FIG.
図１によると、プラズマアーク溶解法を採用した場合と同様に、Ａｌ含有量が４０質量％を超えた辺りから、溶解後の酸素含有量が低下していることがわかる。この結果から、誘導溶解法の場合もプラズマアーク溶解法と同様に、Ｔｉ−Ａｌ系合金のＡｌ含有量が４０質量％以上になると溶解により脱酸反応が進行することがわかる。 According to FIG. 1, it can be seen that the oxygen content after melting decreases from the point where the Al content exceeds 40% by mass, as in the case of employing the plasma arc melting method. From this result, it can be understood that, in the case of the induction melting method, as in the plasma arc melting method, the deoxidation reaction proceeds by dissolution when the Al content of the Ti-Al alloy becomes 40% by mass or more.
・誘導溶解法、フラックス添加有
また、Ａｌ含有量が、４０質量％、４８質量％、５９質量％のＴｉ−Ａｌ系合金について、ＣａＯ−ＣａＦ２フラックス添加による脱酸反応の促進状況を調べるため、水冷銅容器を用いた誘導溶解法によるＴｉ−Ａｌ合金の脱酸を実施した。尚、各溶解において、溶解チャンバー内雰囲気はＡｒ、溶解中の圧力は７．０×１０４Ｐａとし、ＣａＯ−ＣａＦ２フラックス中のフッ化カルシウムの配合量は８０質量％、ＣａＯ−ＣａＦ２フラックスの添加量は、メタル質量の１０％とした。結果を図１に示す。
Induction melting method, a flux added Yes addition, Al content is 40 wt%, 48 wt%, 59 for mass% of Ti-Al alloy, in order to examine the accelerated conditions of deoxidation reaction with CaO-CaF 2 flux added The Ti—Al alloy was deoxidized by induction melting using a water-cooled copper container. In each dissolution, the atmosphere in the dissolution chamber was Ar, the pressure during dissolution was 7.0 × 10 4 Pa, the blending amount of calcium fluoride in the CaO—CaF 2 flux was 80% by mass, and the CaO—CaF 2 flux The amount of added was 10% of the metal mass. The results are shown in FIG.
図１によると、水冷銅容器を用いた誘導溶解法を用いた場合でも、ＣａＯ−ＣａＦ２フラックスを添加した場合は、Ａｌ含有量が、４０質量％、４８質量％、５９質量％の何れの場合においても、ＣａＯ−ＣａＦ２フラックスを添加しない場合に比べ、更に脱酸が促進されていることがわかる。 According to FIG. 1, even when the induction melting method using a water-cooled copper container is used, when the CaO—CaF 2 flux is added, the Al content is any of 40% by mass, 48% by mass, and 59% by mass. Even in the case, it is understood that deoxidation is further promoted as compared with the case where the CaO—CaF 2 flux is not added.
（ＣａＯ−ＣａＦ２フラックス中のフッ化カルシウムの配合量）
Ａｌ含有量が４０質量％のＴｉ−Ａｌ合金を用い、添加するＣａＯ−ＣａＦ２フラックスのフッ化カルシウムの配合量を変えて、あとは全て前記した実施例と同じ条件で、１００ｋＷプラズマアーク炉を用いたプラズマアーク溶解によりＴｉ−Ａｌ合金の脱酸を実施した。尚、ＣａＯ−ＣａＦ２フラックスは、予め溶解前のＴｉ−Ａｌ合金の周囲に敷き詰めた。結果を図２に示す。
(Amount of calcium fluoride in CaO-CaF 2 flux)
Using a Ti—Al alloy with an Al content of 40% by mass, changing the blending amount of calcium fluoride in the CaO—CaF 2 flux to be added, and then using a 100 kW plasma arc furnace under the same conditions as in the previous examples. The Ti-Al alloy was deoxidized by the plasma arc melting used. The CaO—CaF 2 flux was spread around the Ti—Al alloy before melting. The results are shown in FIG.
ＣａＯ−ＣａＦ２フラックスを添加しない場合の溶解後の酸素含有量である５４００ｐｐｍを基準とし、ＣａＯ−ＣａＦ２フラックス添加による脱酸反応促進効果の度合いを調べた。図２によると、酸化カルシウムにフッ化カルシウムを６０〜９０質量％配合したＣａＯ−ＣａＦ２フラックスを添加した場合が、最も顕著な脱酸反応促進効果が得られていることが分かるが、４０質量％以上配合した場合でも大きな脱酸反応促進効果がある。この試験結果から、酸化カルシウムにフッ化カルシウムを３５〜９５質量％配合したＣａＯ−ＣａＦ２フラックスを添加することで脱酸効果が得られることが分かる。尚、図２によると、酸化カルシウムにフッ化カルシウムを３０質量％配合したＣａＯ−ＣａＦ２フラックスを添加した場合は、脱酸が促進されていないことが分かる。これはＣａＯ−ＣａＦ２フラックスの融点が高過ぎて未溶融であるからである。 The 5400ppm oxygen content after dissolution without the addition of CaO-CaF 2 flux as a reference, was examined the degree of deoxidation reaction acceleration effect by CaO-CaF 2 flux added. According to FIG. 2, it can be seen that when CaO—CaF 2 flux containing 60 to 90% by mass of calcium fluoride in calcium oxide is added, the most remarkable deoxidation reaction promoting effect is obtained. Even when blended in an amount of at least%, there is a significant deoxidation reaction promoting effect. From this test result, it can be seen that the deoxidation effect can be obtained by adding CaO—CaF 2 flux containing 35 to 95 mass% of calcium fluoride to calcium oxide. Incidentally, according to FIG. 2, the case of adding CaO-CaF 2 flux was blended 30 wt% of calcium fluoride to calcium oxide, it can be seen that deoxidation is not promoted. This is because the melting point of the CaO—CaF 2 flux is too high and is not melted.
（溶解前後のＴｉ−Ａｌ系合金の質量およびＡｌ含有量の変化）
Ｔｉ−Ａｌ系合金を、１００ｋＷプラズマアーク炉を用いて溶解した時の揮発による材料歩留りを、溶解前後の前記各サンプルの質量およびＡｌ含有量の変化を調べることで評価した。
(Changes in mass and Al content of Ti-Al alloy before and after melting)
The material yield due to volatilization when the Ti—Al based alloy was melted using a 100 kW plasma arc furnace was evaluated by examining the change in mass and Al content of each sample before and after melting.
まず、溶解時間と溶解前後のサンプルの質量変化率の関係を図３に示す。図３によると、溶解前後でサンプルの質量変化は殆どないことがわかる。次に、サンプルのＡｌ濃度（含有量）と溶解前後のサンプルの質量変化率の関係を図４に示す。図４によると、溶解前後でサンプルの質量変化は殆どなく、Ａｌは１００ｋＷプラズマアーク炉を用いた溶解により揮発していないことがわかる。これらの結果から、水冷銅容器を用いた溶解の一例であるプラズマアーク炉を用いた溶解では、Ｔｉ−Ａｌ系合金の溶解時に、合金元素であるＡｌ、更にはＴｉも揮発しないことがわかる。 First, FIG. 3 shows the relationship between the dissolution time and the mass change rate of the sample before and after dissolution. According to FIG. 3, it can be seen that there is almost no change in the mass of the sample before and after dissolution. Next, FIG. 4 shows the relationship between the Al concentration (content) of the sample and the mass change rate of the sample before and after dissolution. According to FIG. 4, there is almost no change in the mass of the sample before and after melting, and it can be seen that Al is not volatilized by melting using a 100 kW plasma arc furnace. From these results, it is understood that in the melting using the plasma arc furnace, which is an example of the melting using the water-cooled copper container, the alloy elements Al and further Ti are not volatilized when the Ti—Al alloy is melted.
Claims (3)
前記Ｔｉ−Ａｌ系合金の酸素含有量を低下させることを特徴とするＴｉ−Ａｌ系合金の脱酸方法。 A Ti—Al-based alloy containing 40 mass% or more of Al produced by using an alloy material made of a titanium material and an aluminum material and containing 0.1 mass% or more in total of oxygen under an atmosphere of 1.33 Pa or more By dissolving and holding by a dissolution method using a water-cooled copper container,
A method for deoxidizing a Ti-Al alloy, wherein the oxygen content of the Ti-Al alloy is reduced.
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| PCT/JP2015/074970 WO2016035824A1 (en) | 2014-09-04 | 2015-09-02 | METHOD FOR DEOXIDIZING Ti-Al ALLOY |
| RU2017110549A RU2673589C2 (en) | 2014-09-04 | 2015-09-02 | Ti-Al ALLOY DEOXIDATION METHOD |
| EP15838357.0A EP3190196B1 (en) | 2014-09-04 | 2015-09-02 | Method for deoxidizing ti-al alloy |
| CN201580046835.3A CN106661670B (en) | 2014-09-04 | 2015-09-02 | The method of deoxidation of Ti-Al systems alloy |
| US15/508,384 US20170283906A1 (en) | 2014-09-04 | 2015-09-02 | METHOD FOR DEOXIDIZING Ti-Al ALLOY |
| AU2015312896A AU2015312896B2 (en) | 2014-09-04 | 2015-09-02 | Method for deoxidizing Ti-Al alloy |
| ZA2017/01496A ZA201701496B (en) | 2014-09-04 | 2017-02-28 | Method for deoxidizing ti-al alloy |
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| EP3586998B1 (en) | 2017-02-23 | 2021-08-11 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method for producing ti-al alloy |
| JP7412197B2 (en) * | 2020-02-03 | 2024-01-12 | 株式会社神戸製鋼所 | Method for manufacturing Ti-Al alloy |
| CN112809013B (en) * | 2020-12-30 | 2022-05-27 | 中国科学院过程工程研究所 | Preparation method of Ti-6Al-4V alloy powder |
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| JP3046349B2 (en) * | 1990-11-14 | 2000-05-29 | ゼネラル・エレクトリック・カンパニイ | Method of treating titanium-aluminum modified with chromium and niobium |
| US5102450A (en) * | 1991-08-01 | 1992-04-07 | General Electric Company | Method for melting titanium aluminide alloys in ceramic crucible |
| JP2989053B2 (en) * | 1991-08-30 | 1999-12-13 | 株式会社神戸製鋼所 | Method for producing low oxygen Ti-Al alloy and low oxygen Ti-Al alloy |
| JP2989060B2 (en) * | 1991-11-15 | 1999-12-13 | 株式会社神戸製鋼所 | Low oxygen Ti-Al alloy and method for producing the same |
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| CN1158397C (en) * | 2001-11-21 | 2004-07-21 | 中国科学院金属研究所 | Process for vacuum induction smelting Ti-Al alloy |
| RU2269584C1 (en) * | 2004-07-30 | 2006-02-10 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Titanium-base alloy |
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