JP6556554B2 - Method for deoxidizing Al-Nb-Ti alloy - Google Patents
Method for deoxidizing Al-Nb-Ti alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims description 107
- 229910045601 alloy Inorganic materials 0.000 title claims description 97
- 229910020012 Nb—Ti Inorganic materials 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 45
- 239000001301 oxygen Substances 0.000 claims description 69
- 229910052760 oxygen Inorganic materials 0.000 claims description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 67
- 239000010955 niobium Substances 0.000 claims description 66
- 238000002844 melting Methods 0.000 claims description 55
- 230000008018 melting Effects 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 54
- 229910052758 niobium Inorganic materials 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 34
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 238000004090 dissolution Methods 0.000 claims description 25
- 230000004907 flux Effects 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 10
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 229910001257 Nb alloy Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910004349 Ti-Al Inorganic materials 0.000 description 9
- 229910004692 Ti—Al Inorganic materials 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000484 niobium oxide Inorganic materials 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- OQPDWFJSZHWILH-UHFFFAOYSA-N [Al].[Al].[Al].[Ti] Chemical compound [Al].[Al].[Al].[Ti] OQPDWFJSZHWILH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021324 titanium aluminide Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011978 dissolution method Methods 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
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- -1 scrap raw material Chemical compound 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 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
- C22C1/026—Alloys based on aluminium
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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
- C22B9/10—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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/00—Alloys based on aluminium
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Description
本発明は、アルミニウム材料、ニオブ材料およびチタン材料よりなる、酸素を合計で０．５質量％以上含有する合金材料を用いて作製したＡｌ−Ｎｂ−Ｔｉ系合金から酸素を除去するＡｌ−Ｎｂ−Ｔｉ系合金の脱酸方法に関するものである。 The present invention removes oxygen from an Al—Nb—Ti-based alloy made using an alloy material made of an aluminum material, a niobium material, and a titanium material and containing 0.5% by mass or more of oxygen in total. The present invention relates to a method for deoxidizing a Ti-based alloy.
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。その中でもＴｉ−Ａｌに更にＮｂを添加し、耐酸化性をより向上させたＴｉ−Ａｌ−Ｎｂ系合金の需要は特に高まりつつある。このような活性金属のチタンを主成分とするＴｉ−Ａｌ−Ｎｂ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ことが不可欠であり、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. Among them, the demand for Ti—Al—Nb alloys in which Nb is further added to Ti—Al to further improve the oxidation resistance is increasing. When manufacturing titanium alloys such as Ti-Al-Nb alloys mainly composed of such active metal titanium, it is indispensable to prevent contamination by oxygen during melting. Melting methods such as (VAR), 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−Ｎｂ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やＮｂ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−Ｎｂ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-described 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-Nb alloy. In addition to Al and Nb, which are alloy elements, Ti also volatilizes during melting and causes loss. That is, in an industrial process, it is extremely difficult to control the Ti—Al—Nb-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−Ｎｂ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ニオブ材料やチタン材料を用いてＴｉ−Ａｌ−Ｎｂ系合金を製造することが有効であるが、高品位なニオブ材料は、高価格であり、特に近年は高騰する傾向にあるため、酸素含有量は多いが価格が安い低級ニオブ、酸化ニオブ鉱石（Ｎｂ２Ｏ５）、スクラップ原料などの比較的低品位なニオブ材料を用いてＴｉ−Ａｌ−Ｎｂ合金を製造したいというニーズが日々高まっている。また、高品位なチタン材料も価格が高く、ニオブ材料同様にスクラップ原料など低品位なチタン材料を使用したいとのニーズも高まっている。 Further, in order to melt a Ti—Al—Nb alloy having a low oxygen content, it is possible to manufacture a Ti—Al—Nb alloy using a high-grade niobium material or a titanium material having a low oxygen content. Although effective, high-quality niobium materials are expensive and particularly tend to soar in recent years, low-grade niobium, niobium oxide ore (Nb 2 O 5 ), scrap with high oxygen content but low price There is a growing need to manufacture Ti—Al—Nb alloys using relatively low grade niobium materials such as raw materials. High-grade titanium materials are also expensive and there is a growing need to use low-grade titanium materials such as scrap raw materials as well as niobium materials.
Ｔｉは活性金属であり、溶解する雰囲気中に存在する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中に溶存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 an extremely strong binding force with oxygen present in the melting atmosphere, measures have been conventionally taken to reduce oxygen taken from the outside during melting and prevent contamination. 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、酸化カルシウム製の坩堝中で、アルミニウム化チタン合金と、メルト中への酸素の取り込みを低減するのに有効な量のニオブ等の金属とからなる装入材料を融解させる段階から成る、γアルミニウム化チタン合金を融解させる方法が記載されているが、単にＴｉ−Ａｌ−Ｎｂ系合金の溶解方法が記載されているだけで、Ｔｉ−Ａｌ−Ｎｂ系合金の脱酸方法に関する技術は記載ばかりか示唆すらされていない。また、ニオブ原料も純度９９．９％以上の高純度品が使用されており、溶解後のＴｉ−Ａｌ−Ｎｂ系合金の酸素濃度も脱酸が必要ない濃度となっている。 Patent Document 1 discloses a step of melting a charging material composed of a titanium aluminide alloy and a metal such as niobium in an amount effective for reducing oxygen uptake into a melt in a crucible made of calcium oxide. A method for melting a γ titanium aluminide alloy is described, but only a method for melting a Ti—Al—Nb alloy is described, and a method for deoxidizing a Ti—Al—Nb alloy is described. The technology is not only mentioned or even suggested. In addition, niobium raw materials are high-purity products having a purity of 99.9% or more, and the oxygen concentration of the Ti—Al—Nb-based alloy after melting is a concentration that does not require deoxidation.
また、特許文献２には、Ｔｉ−Ａｌ系合金を石灰坩堝の中で真空或いは不活性雰囲気中で溶解し、この溶融Ｔｉ−Ａｌ系合金にＣａ或いはＣａ含有合金を添加して、脱酸処理を行うＴｉ−Ａｌ系合金の製造方法が記載されている。この特許文献２には、確かにＴｉ−Ａｌ系合金の脱酸方法に関する技術が記載されているものの、酸素含有量が高いニオブ材料を用いることばかりか、ニオブ材料を用いることすら記載されておらず、また、示唆すらされていない。
In
特許文献３には、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系合金を製造する方法が記載されている。しかしながら、この特許文献３にも、ニオブ材料を用いることすら記載されておらず、Ｔｉ−Ａｌ−Ｎｂ系合金の脱酸方法については記載も示唆もされていない。また、特許文献３に記載された技術によれば、Ｃａ添加溶解、並びにＣａ除去および均質化のための溶解の２工程を要すると共に、残留Ｃａの完全な排除ができないため、製造コスト時間の増大と共に、残留Ｃａによる各種特性の変化すら懸念される。 In Patent Document 3, high purity, low oxygen Ti-Al is obtained by deoxidizing with Ca, evaporating and removing excess Ca, and non-contaminating homogeneous dissolution in the melting of an alloy system mainly composed of Ti-Al. A method for producing a base alloy is described. However, this Patent Document 3 does not even describe the use of a niobium material, nor does it describe or suggest a deoxidation method for a Ti—Al—Nb alloy. In addition, according to the technique described in Patent Document 3, two steps of dissolution for addition of Ca and dissolution for removal and homogenization of Ca are required, and residual Ca cannot be completely eliminated, resulting in an increase in manufacturing cost time. At the same time, there are concerns about changes in various characteristics due to residual Ca.
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ニオブ材料を用いて、目標の組成でしかも酸素含有量が少ないＴｉ−Ａｌ−Ｎｂ系合金を得るにあたり、まずはＡｌを主成分とする酸素含有量の少ないＡｌ−Ｎｂ−Ｔｉ系合金を製造することに着目し、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Ａｌ−Ｎｂ−Ｔｉ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 niobium material having a high oxygen content to obtain a Ti-Al-Nb alloy having a target composition and a low oxygen content. At first, focusing on producing an Al—Nb—Ti alloy having a low oxygen content with Al as a main component, an Al—Nb—Ti alloy that can be easily produced without using a high vacuum atmosphere. It is an object of the present invention to provide a deoxidation method.
本発明のＡｌ−Ｎｂ−Ｔｉ系合金の脱酸方法は、アルミニウム材料、ニオブ材料およびチタン材料よりなる、酸素を合計で０．５質量％以上含有する合金材料を用いて作製した、Ａｌを５０〜７５質量％、Ｎｂを５〜３０質量％、且つ、ＡｌとＮｂの合計量で８０質量％以下を含有するＡｌ−Ｎｂ−Ｔｉ系合金を、１９００Ｋ以上の温度、１．３３Ｐａ〜２．６７×１０５Ｐａ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、酸素含有量を低下させることを特徴とする。 The method for deoxidizing an Al—Nb—Ti alloy according to the present invention uses an aluminum material, a niobium material, and a titanium material, which is made of an alloy material containing a total of 0.5 mass% or more of oxygen. An Al—Nb—Ti-based alloy containing 75% by mass, 5% to 30% by mass of Nb, and 80% by mass or less in terms of the total amount of Al and Nb is at a temperature of 1900K or more, 1.33 Pa to 2.67. In an atmosphere of × 10 5 Pa, the oxygen content is reduced by dissolving and holding by a dissolution method using a water-cooled copper container.
更に、前記水冷銅容器を用いた溶解法による前記Ａｌ−Ｎｂ−Ｔｉ系合金の溶解中に、酸化カルシウムにフッ化カルシウムを０〜９５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。 Furthermore, it is preferable to add CaO—CaF 2 flux in which 0 to 95% by mass of calcium fluoride is mixed with calcium oxide during dissolution of the Al—Nb—Ti alloy by the melting method using the water-cooled copper container. .
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Ａｌ−Ｎｂ−Ｔｉ系合金の脱酸方法によると、融体中のＡｌの含有量を５０〜７５質量％と高濃度とすることで、酸素含有量が高い低品位で廉価なニオブ材料を用いて、Ａｌ、Ｎｂ、Ｔｉが溶解中に揮発ロスすることが殆どなく、目標の組成で、しかも酸素含有量が少ないＡｌ−Ｎｂ−Ｔｉ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。そして、上記酸素含有量が少ないＡｌ−Ｎｂ−Ｔｉ系合金を酸素含有量が少ないＴｉと適量混合することで、比較的低コストで、所望のＴｉを主成分とするＴｉ−Ａｌ−Ｎｂ系合金を得ることができるようになる。 According to the deoxidation method of the Al—Nb—Ti alloy of the present invention, the low content and low price niobium with a high oxygen content can be obtained by setting the Al content in the melt as high as 50 to 75% by mass. Using materials, Al, Nb, Ti hardly loses volatilization during melting, and it is easy even if Al-Nb-Ti alloy with a target composition and low oxygen content is not used in a high vacuum atmosphere. Can be manufactured. Then, by mixing an appropriate amount of the above-described Al—Nb—Ti alloy having a low oxygen content with Ti having a low oxygen content, a Ti—Al—Nb alloy having the desired Ti as a main component at a relatively low cost. You will be able to get
本発明者らは、前記した酸素含有量が高い低品位なニオブ材料を用いて、目標の組成でしかも酸素含有量が少ないＴｉ-Ａｌ−Ｎｂ系合金（活性金属のチタンを主成分とするＴｉ-Ａｌ−Ｎｂ系合金）を得るため、鋭意検討を行ってきた。 The present inventors have used the above-described low-grade niobium material having a high oxygen content, and a Ti—Al—Nb-based alloy having a target composition and a low oxygen content (Ti containing an active metal titanium as a main component). -Al-Nb-based alloys) have been studied earnestly.
その結果、予め所望の組成、すなわちチタンを主成分とする合金組成に制御しつつ、並行して酸素含有量を低減させることは技術的・コスト的に難しい一方、その工程を分割し、酸素含有量が少なく、且つアルミを主成分とするＡｌ-Ｎｂ-Ｔｉ合金を作製した後、当該酸素含有量の少ないＡｌ-Ｎｂ-Ｔｉ合金と通常の製法で得られる酸素含有量の少ない純Ｔｉを適量混合するようにすれば、比較的容易且つ低コストで所望の組成のチタンを主成分とするＴｉ-Ａｌ−Ｎｂ系合金を得ることができるのではないかとの考えに至った。 As a result, while it is difficult to reduce the oxygen content in parallel while controlling the desired composition in advance, that is, the alloy composition containing titanium as a main component, it is difficult in terms of technology and cost. After producing an Al-Nb-Ti alloy with a small amount and containing aluminum as a main component, an appropriate amount of the Al-Nb-Ti alloy with a low oxygen content and pure Ti with a low oxygen content obtained by a normal manufacturing method It came to the idea that a Ti—Al—Nb-based alloy containing titanium having a desired composition as a main component could be obtained relatively easily and at low cost if mixed.
そして、本発明者らは、合金中に高濃度のＡｌを含有する組成範囲において固溶し得る酸素濃度（固溶限）が低下することを見出し、低級ニオブ、酸化ニオブ鉱石（ＮｂＯＸ）、スクラップ原料などの酸素を多く含有する低品位なニオブ材料やチタン材料を用いて、Ａｌ、Ｎｂ、Ｔｉが揮発ロスすることなく目標の組成で、しかも酸素含有量が少ないＡｌ−Ｎｂ−Ｔｉ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。 Then, the present inventors have found that the oxygen concentration (solid solubility limit) that can be dissolved in a composition range containing a high concentration of Al in the alloy decreases, and lower niobium, niobium oxide ore (NbO x ), Using a low-grade niobium material or titanium material containing a large amount of oxygen such as scrap raw material, Al-Nb-Ti alloy with a target composition and low oxygen content with no volatilization loss of Al, Nb, Ti In order to find a method that can be easily manufactured without using a high-vacuum atmosphere, intensive studies were conducted.
すなわち、融体中のＡｌの含有量を５０〜７５質量％と高くすることで、低品位なニオブ材料やチタン材料を用いて作製したＡｌ−Ｎｂ−Ｔｉ系合金であっても、高真空雰囲気としなくても水冷銅容器を用いた溶解で脱酸反応が進行し、また、Ａｌ、Ｎｂ、Ｔｉの揮発ロスが殆どなく目標の組成の低酸素Ａｌ−Ｎｂ−Ｔｉ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。 That is, even if it is an Al—Nb—Ti alloy produced using a low-grade niobium material or a titanium material by increasing the Al content in the melt to 50 to 75 mass%, a high vacuum atmosphere Even if it does not, deoxidation reaction proceeds by dissolution using a water-cooled copper container, and there is almost no volatilization loss of Al, Nb, Ti, and a low-oxygen Al—Nb—Ti alloy having a target composition can be easily produced. As a result, the present invention has been completed.
また、Ａｌ−Ｎｂ−Ｔｉ系合金を溶解する前或いは溶解中に、チタン中で溶存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も併せて見出した。 Further, before or during the dissolution of the Al—Nb—Ti alloy, by adding CaO—CaF 2 flux having a specific component composition not dissolved in titanium as a deoxidation reaction accelerator, the deoxidation reaction is We also found that the process progressed more reliably.
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Ａｌ−Ｎｂ−Ｔｉ系合金の脱酸方法は、アルミニウム材料、ニオブ材料およびチタン材料よりなる、酸素を合計で０．５質量％以上含有する合金材料を用いて作製した、Ａｌを５０〜７５質量％、Ｎｂを５〜３０質量％、且つ、ＡｌとＮｂの合計量で８０質量％以下を含有するＡｌ−Ｎｂ−Ｔｉ系合金を、１９００Ｋ以上の温度、１．３３Ｐａ〜２．６７×１０５Ｐａ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、酸素含有量を低下させる方法であって、前記ニオブ材料としては、低品位な、低級ニオブ、酸化ニオブ鉱石（ＮｂＯｘ）、スクラップ原料などを、前記チタン材料としては、酸化チタン（ＴｉＯＸ）やスクラップ原料などを用いることができる。 The method for deoxidizing an Al—Nb—Ti alloy according to the present invention uses an aluminum material, a niobium material, and a titanium material, which is made of an alloy material containing a total of 0.5 mass% or more of oxygen. An Al—Nb—Ti-based alloy containing 75% by mass, 5% to 30% by mass of Nb, and 80% by mass or less in terms of the total amount of Al and Nb is at a temperature of 1900K or more, 1.33 Pa to 2.67. It is a method of reducing the oxygen content by melting and holding 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 in an atmosphere of × 10 5 Pa. Examples of the niobium material, a low-grade, lower niobium, niobium oxide ore (NbO x), and scrap material, as the titanium material, titanium oxide (TiO X) or scrap material such as It can be used.
Ａｌ−Ｎｂ−Ｔｉ系合金の作製に、低品位な、低級ニオブ、酸化ニオブ鉱石（ＮｂＯｘ）、スクラップ原料などの酸素含有量が多いニオブ材料を用いる理由は、これらニオブ材料が、高品位な原料に比べて、廉価であり調達し易いからである。また、アルミニウム材料、ニオブ材料およびチタン材料よりなる合金材料の酸素の合計含有量を０．５質量％以上としたのは、合金材料中の酸素の合計含有量が０．５質量％未満であれば、酸素の含有量は僅かであり、希釈化や簡易的な精錬を実施することで低酸素Ａｌ−Ｎｂ−Ｔｉ系合金を容易に得ることができるからである。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、３０．０質量％程度であると考えられる。 The reason for using low-grade, low-grade niobium, niobium oxide ore (NbO x ), scrap materials and other oxygen-containing niobium materials for the production of Al—Nb—Ti-based alloys is because these niobium materials are high-grade. This is because it is cheaper and easier to procure than raw materials. Also, the total oxygen content of the alloy material made of aluminum material, niobium material and titanium material is 0.5 mass% or more if the total oxygen content in the alloy material is less than 0.5 mass%. For example, the oxygen content is small, and a low-oxygen Al—Nb—Ti-based alloy can be easily obtained by dilution or simple refining. 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 30.0% by mass.
また、前記アルミニウム材料、ニオブ材料およびチタン材料よりなる合金材料を用いて作製したＡｌ−Ｎｂ−Ｔｉ系合金のＡｌ含有量を５０〜７５質量％、Ｎｂ含有量を５〜３０質量％、且つ、ＡｌとＮｂの合計量で８０質量％以下とした理由は、Ａｌ−Ｎｂ−Ｔｉ系合金中のＡｌ含有量が５０質量％以上、Ｎｂの含有量が５質量％以上であれば、高真空雰囲気下ではなくて、１．３３Ｐａ〜２．６７×１０５Ｐａ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、Ａｌ−Ｎｂ−Ｔｉ系合金の脱酸反応が進行するからである。また、溶解中の圧力を１．３３Ｐａ〜２．６７×１０５Ｐａとした理由は、Ａｌ、Ｎｂ、Ｔｉの揮発ロスがなく、且つ、溶湯の飛散による歩留り低下を防止できるのが、この範囲の圧力であるからである。 Further, the Al content of the Al—Nb—Ti alloy produced using the alloy material made of the aluminum material, niobium material and titanium material is 50 to 75 mass%, the Nb content is 5 to 30 mass%, and The reason why the total amount of Al and Nb is 80% by mass or less is that if the Al content in the Al—Nb—Ti-based alloy is 50% by mass or more and the Nb content is 5% by mass or more, a high vacuum atmosphere Even under an atmosphere of 1.33 Pa to 2.67 × 10 5 Pa, not by the bottom, 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, etc. This is because the deoxidation reaction of the Nb—Ti alloy proceeds. Moreover, the reason why the pressure during melting is 1.33 Pa to 2.67 × 10 5 Pa is that there is no volatilization loss of Al, Nb, and Ti, and it is possible to prevent a decrease in yield due to scattering of the molten metal. This is because of the pressure.
この脱酸反応は、酸素固溶量の少ない高Ａｌ含有領域においてのみ発現する現象であり、Ａｌ含有量が高くなる程、酸素固溶限が少なくなることは、以下のＴｉ−Ａｌ−Ｏ３元系状態図に示唆されている（Ｘ．Ｌ．Ｌｉ，Ｒ．Ｈｉｌｌｅｌ，Ｆ．Ｔｅｙｓｓａｎｄｉｅｒ，Ｓ．Ｋ．Ｃｈｏｉ，ａｎｄ Ｆ．Ｊ．Ｊ．Ｖａｎ Ｌｏｏ，Ａｃｔａ Ｍｅｔａｌｌ．Ｍａｔｅｒ．４０［１１］３１４７−３１５７（１９９２））。また、この脱酸反応は、液相において発現する現象でもあり、Ａｌ−Ｎｂ−Ｔｉ系合金の場合は、合金融体中のＡｌ活量が高くなると脱酸反応がより顕著に進行する。Ａｌ−Ｎｂ−Ｔｉ系合金のＡｌ含有量が５０〜７５質量％、Ｎｂの含有量が５〜３０質量％、且つ、ＡｌとＮｂの合計量で８０質量％以下であれば、概ね１９００Ｋ以上の温度で、脱酸反応が進行する。 This deoxidation reaction is a phenomenon that appears only in a high Al-containing region with a small amount of oxygen solid solution. The higher the Al content, the smaller the oxygen solid solution limit is, the following Ti-Al-O3 element. It is suggested in the system phase diagram (XL Li, R. Hillel, F. Teyssandier, SK Choi, and F. J. J. Van Loo, Acta Metal. Mater. 40 [11] 3147- 3157 (1992)). Moreover, this deoxidation reaction is also a phenomenon that develops in the liquid phase. In the case of an Al—Nb—Ti alloy, the deoxidation reaction proceeds more significantly when the Al activity in the combined financial body increases. If the Al content of the Al—Nb—Ti-based alloy is 50 to 75% by mass, the Nb content is 5 to 30% by mass, and the total amount of Al and Nb is 80% by mass or less, approximately 1900K or more. The deoxidation reaction proceeds at temperature.
また、Ａｌ−Ｎｂ−Ｔｉ系合金のＡｌ含有量の上限を７５質量％、Ｎｂ含有量の上限を３０質量％、且つ、ＡｌとＮｂの合計量で８０質量％以下とした理由は、Ａｌ−Ｎｂ−Ｔｉ系合金はＮｂおよびＴｉ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、ＡｌおよびＮｂの含有量が多くなり過ぎるとＴｉの割合が少なくなりＡｌ−Ｎｂ−Ｔｉ系合金ということができなくなるからである。 The reason why the upper limit of the Al content of the Al—Nb—Ti-based alloy is 75% by mass, the upper limit of the Nb content is 30% by mass, and the total amount of Al and Nb is 80% by mass or less is that Al— Since the Nb-Ti alloy contains other alloy elements other than Nb and Ti and impurities such as oxygen, if the content of Al and Nb is excessively large, the proportion of Ti decreases and the Al-Nb-Ti alloy is referred to. Because it becomes impossible.
また、本発明のＡｌ−Ｎｂ−Ｔｉ系合金の脱酸方法は、Ａｌ、Ｎｂ、Ｔｉの揮発ロスが殆どなく、酸素含有量を低下させる方法であると説明したが、揮発ロスが殆どないとは、溶解前後でのＡｌ含有量の差が１．０質量％以下、Ｎｂ含有量の差が０．５質量％以下であることを指す。 Moreover, although the deoxidation method of the Al-Nb-Ti alloy of the present invention is described as a method of reducing the oxygen content with almost no volatilization loss of Al, Nb, Ti, there is almost no volatilization loss. Means that the difference in Al content before and after dissolution is 1.0 mass% or less, and the difference in Nb content is 0.5 mass% or less.
また、Ａｌ−Ｎｂ−Ｔｉ系合金の脱酸を行うにあたり、脱酸反応促進剤として、ＣａＯ単体のフラックス、または酸化カルシウムにフッ化カルシウムを０質量％超９５質量％以下配合したＣａＯ−ＣａＦ２フラックスを添加することで脱酸反応がより促進される。 Further, when deoxidizing the Al—Nb—Ti alloy, as a deoxidation reaction accelerator, CaO single flux or CaO—CaF 2 in which calcium fluoride is blended with calcium oxide in an amount of more than 0 mass% and not more than 95 mass%. The deoxidation reaction is further promoted by adding the flux.
また、Ａｌ−Ｎｂ−Ｔｉ系合金中に固溶しない、ＣａＯ単体のフラックス、または酸化カルシウムにフッ化カルシウムを０質量％超９５質量％以下配合したＣａＯ−ＣａＦ２フラックスを添加することにより、Ａｌ−Ｎｂ−Ｔｉ系合金溶解時に生成した脱酸生成物のＡｌ２Ｏ３がＣａＯと化合物を生成またはＣａＯ−ＣａＦ２中に溶解してＡｌ２Ｏ３活量が低下し、更に脱酸反応が促進される。 Further, by adding a CaO single flux that does not form a solid solution in the Al—Nb—Ti-based alloy, or a CaO—CaF 2 flux in which calcium fluoride is added to calcium oxide in an amount of more than 0% by mass to 95% by mass, Al The deoxidation product Al 2 O 3 produced during dissolution of the —Nb—Ti-based alloy produces a compound with CaO or dissolves in CaO—CaF 2 to lower the activity of Al 2 O 3 , and further the deoxidation reaction Promoted.
前記脱酸反応が進行するためには、Ａｌ−Ｎｂ−Ｔｉ系合金中に存在しているＡｌ２Ｏ３と添加フラックスが接触する必要があると考えられる。Ａｌ−Ｎｂ−Ｔｉ系合金の比重は、高比重のＮｂが添加されているため、Ｔｉ−Ａｌ２元系合金の比重よりも大きくなり、Ａｌ−Ｎｂ−Ｔｉ系合金と、Ａｌ２Ｏ３および添加フラックスの分離が促進され、結果的に、Ａｌ２Ｏ３とフラックスが接触しやすくなると推測される。 In order for the deoxidation reaction to proceed, it is considered that Al 2 O 3 present in the Al—Nb—Ti-based alloy needs to come into contact with the added flux. The specific gravity of the Al—Nb—Ti alloy is higher than that of the Ti—Al binary alloy because of the high specific gravity of Nb added, and the Al—Nb—Ti alloy, Al 2 O 3 and the addition are added. It is presumed that separation of the flux is promoted, and as a result, Al 2 O 3 and the flux are likely to come into contact with each other.
また、フッ化カルシウムが０質量％の場合、つまりＣａＯ単体のフラックスは高融点であり、Ａｌ−Ｎｂ−Ｔｉ系合金の融点程度の温度では溶融しないが、Ａｌ−Ｎｂ−Ｔｉ系合金中に存在しているＡｌ２Ｏ３と接触すると低融点のＣａＯ−Ａｌ２Ｏ３系化合物を生成し、Ａｌ２Ｏ３活量を低下させ、更なる脱酸促進が可能であるため、Ａｌ−Ｎｂ−Ｔｉ系合金の融点以上のフラックスであるが使用可能である。 When calcium fluoride is 0% by mass, that is, the flux of CaO alone has a high melting point and does not melt at a temperature about the melting point of the Al—Nb—Ti alloy, but exists in the Al—Nb—Ti alloy. When it comes into contact with Al 2 O 3 , a low melting point CaO—Al 2 O 3 -based compound is generated, Al 2 O 3 activity is lowered, and further deoxidation promotion is possible. It is possible to use a flux that is higher than the melting point of the Ti-based alloy.
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、ＣａＯ単体のフラックス、または酸化カルシウムにフッ化カルシウムを０質量％超９５質量％以下配合したＣａＯ−ＣａＦ２フラックスを採用する。 On the other hand, when the blending amount of calcium fluoride exceeds 95% by mass, contamination with fluorine occurs. Therefore, in the present invention, a CaO single flux or a CaO—CaF 2 flux in which calcium fluoride is mixed with calcium oxide in an amount of more than 0% by mass and 95% by mass or less is employed.
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.
（Ａｌ−Ｎｂ−Ｔｉ系合金中のＡｌ含有量と溶解前後の酸素含有量の関係）
アルミニウム材料、ニオブ材料およびチタン材料（酸化チタンまたは金属チタン）からなる合金材料を用いて、酸素含有量が４〜３０質量％の合金元素の含有量が様々なＡｌ−Ｎｂ−Ｔｉ系合金を作製した。作製したＡｌ−Ｎｂ−Ｔｉ系合金系合金の脱酸を、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。尚、プラズマガスはＡｒのみを使用し、溶解中の圧力は１．２０×１０５Ｐａとした。
(Relation between Al content in Al-Nb-Ti alloy and oxygen content before and after dissolution)
Using an alloy material composed of an aluminum material, a niobium material, and a titanium material (titanium oxide or metal titanium), an Al—Nb—Ti alloy with various oxygen content of 4 to 30% by mass is produced. did. Deoxidation of the produced Al—Nb—Ti-based alloy-based alloy was performed by melting in a 100 kW plasma arc furnace using a water-cooled copper container and holding it thereafter. Note that only Ar was used as the plasma gas, and the pressure during melting was 1.20 × 10 5 Pa.
Ａｌ−Ｎｂ−Ｔｉ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３０質量％、４５質量％、６０質量％のＡｌ−Ｎｂ−Ｔｉ系合金をそれぞれ用いて作製したサンプルとした。Ａｌ含有量が３０質量％、６０質量％のＡｌ−Ｎｂ−Ｔｉ系合金を用いたサンプルについては、チタン材料として酸化チタンと金属チタンを用いたサンプルを両方準備したが、Ａｌ含有量が４５質量％のＡｌ−Ｎｂ−Ｔｉ系合金を用いたサンプルについては、チタン材料として酸化チタンを用いたサンプルのみを準備した。図１，２には、酸化チタンを用いたサンプルは●印で、金属チタンを用いたサンブルは■印で、それぞれ表す。尚、これらＡｌ−Ｎｂ−Ｔｉ系合金のＮｂ含有量は、表１に示すように１０〜２０質量％の範囲である。 In order to investigate the influence of the Al content of the Al—Nb—Ti alloy on the deoxidation reaction by dissolution, Al—Nb—Ti alloys having an Al content of 30% by mass, 45% by mass, and 60% by mass were used. A sample was prepared. For samples using Al-Nb-Ti alloys with an Al content of 30% by mass and 60% by mass, both samples using titanium oxide and metal titanium were prepared as titanium materials, but the Al content was 45% by mass. As for the sample using the Al—Nb—Ti based alloy, only the sample using titanium oxide as the titanium material was prepared. In FIGS. 1 and 2, samples using titanium oxide are indicated by ●, and samples using metal titanium are indicated by ■. In addition, as shown in Table 1, the Nb content of these Al—Nb—Ti alloys is in the range of 10 to 20% by mass.
Ａｌ−Ｎｂ−Ｔｉ系合金中のＡｌ濃度（Ａｌ含有量）と溶解前後の酸素濃度（酸素含有量）の関係を図１，２に示す。矢印の上側（基端側）が溶解前、下側（先端側）が溶解後を示す。尚、図１，２では、Ａｌ含有量が３０質量％、６０質量％のＡｌ−Ｎｂ−Ｔｉ系合金を用いたサンプルについては、●印と■印を見やすいよう左右に多少ずらせてプロットしている。 The relationship between the Al concentration (Al content) in the Al—Nb—Ti-based alloy and the oxygen concentration (oxygen content) before and after melting is shown in FIGS. The upper side (base end side) of the arrow indicates before dissolution, and the lower side (tip end side) indicates after dissolution. In FIGS. 1 and 2, the samples using Al-Nb-Ti alloys with an Al content of 30% by mass and 60% by mass are plotted slightly shifted left and right so that the ● and ■ marks can be seen easily. Yes.
Ａｌ−Ｎｂ−Ｔｉ系合金については、概ね０．１質量％以下の酸素含有量が求められているが、図１，２によると、Ａｌ含有量が３０質量％および４５質量％のサンプルの溶解後の酸素含有量は、全て０．１質量％以下になっておらず、酸素含有量が０．１質量％以下という条件を満たしていない。一方、Ａｌ含有量が６０質量％のサンプルの溶解後の酸素含有量は、チタン材料として金属チタンを用いた場合は勿論、酸化チタンを用いた場合も、０．１質量％以下になっており、酸素含有量が０．１質量％以下という条件を満たしている。 For Al—Nb—Ti alloys, an oxygen content of approximately 0.1% by mass or less is required. According to FIGS. 1 and 2, dissolution of samples having an Al content of 30% by mass and 45% by mass is achieved. The subsequent oxygen content is not 0.1% by mass or less, and does not satisfy the condition that the oxygen content is 0.1% by mass or less. On the other hand, the oxygen content after dissolution of a sample having an Al content of 60% by mass is 0.1% by mass or less when titanium oxide is used as well as when titanium metal is used as the titanium material. The oxygen content is 0.1% by mass or less.
Ａｌ脱酸はチタン合金中のＡｌ活量に支配されており、Ａｌ活量はＡｌ含有量と対数的な相関関係があるとされている。溶解後の酸素含有量とＡｌ含有量の関係は、Ｍ．Ｍａｅｄａ ｅｔ ａｌ．Ｍａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ａ２３９−２４０（１９９７）２７６−２８０によると、図１に示す破線のような関係になると想定される。この破線を基に推定すると、Ａｌ含有量５０質量％を境に、酸素含有量が０．１質量％以下となると考えられる。 Al deoxidation is governed by the Al activity in the titanium alloy, and the Al activity is assumed to have a logarithmic correlation with the Al content. The relationship between the oxygen content after dissolution and the Al content is as follows. Maeda et al. According to Material Science and Engineering A239-240 (1997) 276-280, it is assumed that the relationship is as shown by the broken line in FIG. If estimated based on this broken line, the oxygen content is considered to be 0.1 mass% or less with the Al content of 50 mass% as a boundary.
（溶解前の配合合金濃度と溶解後の合金濃度の関係）
また、Ａｌ−Ｎｂ−Ｔｉ系合金の溶解（脱酸）前の配合合金濃度と、溶解（脱酸）後の合金濃度の関係についても併せて調査した。表１に、Ａｌ−Ｎｂ−Ｔｉ系合金の溶解前のＡｌおよびＮｂの含有量と、溶解後のＡｌおよびＮｂの含有量の関係を示す。尚、Ｎｏ．の末尾に「ａ」を記載したものは、チタン材料として酸化チタンを用いたものを、Ｎｏ．の末尾に「ｂ」を記載したものは、チタン材料として金属チタンを用いたものを、それぞれ示す。
(Relationship between compound alloy concentration before melting and alloy concentration after melting)
Moreover, the relationship between the alloy concentration of the Al—Nb—Ti-based alloy before dissolution (deoxidation) and the alloy concentration after dissolution (deoxidation) was also investigated. Table 1 shows the relationship between the contents of Al and Nb before melting of the Al—Nb—Ti alloy and the contents of Al and Nb after melting. No. In the case where “a” is written at the end of “No.”, no. "B" at the end of each indicates that using titanium metal as the titanium material.
Ａｌ含有量が３０質量％のＡｌ−Ｎｂ−Ｔｉ系合金の場合は、Ａｌが２．０〜２．２質量％、Ｎｂが０．８〜１．４質量％となっており、溶解後は目標とする組成から乖離していた。また、Ａｌ含有量が４５質量％のＴＡｌ−Ｎｂ−Ｔｉ系合金の場合は、Ａｌが０．８質量％、Ｎｂが０．４質量％となっており、溶解後は目標とする組成からの乖離は小さいものの、これらはＡｌの含有量が少ないため、前記の通り、酸素含有量が０．１質量％以下になっていない。 In the case of an Al-Nb-Ti alloy having an Al content of 30% by mass, Al is 2.0 to 2.2% by mass and Nb is 0.8 to 1.4% by mass. Deviated from the target composition. Further, in the case of a TAl—Nb—Ti alloy with an Al content of 45% by mass, Al is 0.8% by mass and Nb is 0.4% by mass. Although the divergence is small, since the content of Al is small, as described above, the oxygen content is not less than 0.1% by mass.
これに対し、Ａｌ含有量が６０質量％のＡｌ−Ｎｂ−Ｔｉ系合金の場合は、溶解後は、Ａｌが０．４〜０．７質量％、Ｎｂが０．２〜０．３質量％の乖離に止まっている。この結果は、Ａｌ含有量が６０質量％のＡｌ−Ｎｂ−Ｔｉ系合金の場合は、Ａｌの含有量が、全ての酸化Ｎｂが還元できるだけの十分な含有量であったことを示している。 On the other hand, in the case of an Al—Nb—Ti alloy having an Al content of 60% by mass, Al is 0.4 to 0.7% by mass and Nb is 0.2 to 0.3% by mass after melting. The divergence has stopped. This result shows that, in the case of an Al—Nb—Ti alloy with an Al content of 60% by mass, the Al content was sufficient to reduce all the oxidized Nb.
・フラックスを添加した実施例
（Ａｌ−Ｎｂ−Ｔｉ系合金中のＡｌ含有量と溶解前後の酸素含有量の関係）
アルミニウム材料、ニオブ材料（酸化ニオブ）、チタン材料からなる合金材料を用いて、表２に示す合金元素の含有量が異なる２種のＡｌ−Ｎｂ−Ｔｉ系合金を作製した。作製した２種のＡｌ−Ｎｂ−Ｔｉ系合金を水冷銅容器を用いた１０ｋＷプラズマアーク炉で溶解し、脱酸反応促進剤としてフラックスをそれぞれ添加し、その後保持することにより、Ａｌ−Ｎｂ−Ｔｉ系合金の脱酸を実施した。尚、プラズマガスはＡｒのみを使用し、溶解中の圧力は１．２０×１０５Ｐａとした。
・ Examples with added flux (Relation between Al content in Al-Nb-Ti alloy and oxygen content before and after dissolution)
Two types of Al—Nb—Ti alloys having different alloy element contents shown in Table 2 were prepared using an alloy material made of an aluminum material, a niobium material (niobium oxide), and a titanium material. The prepared two types of Al—Nb—Ti-based alloys were dissolved in a 10 kW plasma arc furnace using a water-cooled copper vessel, and flux was added as a deoxidation reaction accelerator, and then retained, thereby maintaining Al—Nb—Ti. Deoxidation of the system alloy was performed. Note that only Ar was used as the plasma gas, and the pressure during melting was 1.20 × 10 5 Pa.
添加したフラックスは、酸化カルシウムにフッ化カルシウムを８０質量％配合したＣａＯ−ＣａＦ２フラックスと、フッ化カルシウムを配合しないＣａＯ単体のフラックスのそれぞれ２種である。 The added flux is two kinds of CaO—CaF 2 flux in which 80% by mass of calcium fluoride is blended with calcium oxide, and a CaO single flux in which calcium fluoride is not blended.
Ａｌ−Ｎｂ−Ｔｉ系合金の溶解後のＡｌ濃度（Ａｌ含有量）と酸素濃度（酸素含有量）の関係を図３，４および表２に示す。尚、図３，４にはフラックスを添加しない実施例についても併せて表示している。 3 and 4 and Table 2 show the relationship between the Al concentration (Al content) and the oxygen concentration (oxygen content) after dissolution of the Al-Nb-Ti alloy. 3 and 4 also show an example in which no flux is added.
前記したように、Ａｌ−Ｎｂ−Ｔｉ系合金については、概ね０．１質量％以下の酸素含有量が求められている。フラックスを添加しないＮｏ．１のサンプルでもＡｌ含有量が６０質量％であるため、溶解後の酸素含有量は０．０７６質量％で、酸素含有量が０．１質量％以下という条件を満たしているが、ＣａＯ単体のフラックスを添加したＮｏ．４のサンプルでは、溶解後の酸素含有量は０．０３６質量％、酸化カルシウムにフッ化カルシウムを８０質量％配合したＣａＯ−ＣａＦ２フラックスを添加したＮｏ．５のサンプルでは、溶解後の酸素含有量は０．０１８質量％と、更に脱酸が促進されていることが分かる。 As described above, an Al-Nb-Ti-based alloy is required to have an oxygen content of approximately 0.1% by mass or less. No addition of flux. Even in the sample 1, since the Al content is 60% by mass, the dissolved oxygen content is 0.076% by mass and the oxygen content is 0.1% by mass or less. No. with added flux In the sample No. 4, the dissolved oxygen content was 0.036% by mass, and No. 2 in which CaO—CaF 2 flux containing calcium fluoride in 80% by mass was added to calcium oxide. In sample No. 5, the oxygen content after dissolution was 0.018% by mass, indicating that deoxidation was further promoted.
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| AU2015344310A AU2015344310B2 (en) | 2014-11-04 | 2015-11-04 | Method for deoxidizing Al-Nb-Ti alloy |
| CN201580058014.1A CN107148484B (en) | 2014-11-04 | 2015-11-04 | The method of deoxidation of Al-Nb-Ti system alloy |
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