WO2018155658A1 - Procédé de production d'alliage de ti-al - Google Patents

Procédé de production d'alliage de ti-al Download PDF

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Publication number
WO2018155658A1
WO2018155658A1 PCT/JP2018/006823 JP2018006823W WO2018155658A1 WO 2018155658 A1 WO2018155658 A1 WO 2018155658A1 JP 2018006823 W JP2018006823 W JP 2018006823W WO 2018155658 A1 WO2018155658 A1 WO 2018155658A1
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Prior art keywords
ingot
mass
alloy
flux
melting
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PCT/JP2018/006823
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English (en)
Japanese (ja)
Inventor
史晃 工藤
大介 松若
石田　斉
哲史 出浦
Original Assignee
株式会社神戸製鋼所
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Priority claimed from JP2017032273A external-priority patent/JP6794598B2/ja
Priority claimed from JP2017197905A external-priority patent/JP6756078B2/ja
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to EP18756604.7A priority Critical patent/EP3586998B1/fr
Priority to US16/487,182 priority patent/US11377714B2/en
Publication of WO2018155658A1 publication Critical patent/WO2018155658A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/041—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for vertical casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/108—Feeding additives, powders, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • 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
    • C22B9/16—Remelting metals
    • C22B9/20—Arc remelting
    • 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

Definitions

  • the present invention provides a high-grade or low-oxygen Ti—Al alloy by adding an aluminum raw material and a flux to a low-grade titanium raw material such as titanium oxide (TiO 2 ) such as lower sponge titanium, scrap titanium, and rutile ore.
  • a low-grade titanium raw material such as titanium oxide (TiO 2 ) such as lower sponge titanium, scrap titanium, and rutile ore.
  • TiO 2 titanium oxide
  • the present invention relates to a method for producing a Ti—Al-based alloy.
  • VAR vacuum arc melting method
  • EB electron beam melting method
  • PAM plasma arc melting method
  • VAR vacuum arc melting method
  • VIM vacuum induction melting
  • CCIM water-cooled copper induction melting
  • high-quality raw materials with low oxygen content are used as titanium raw materials for melting Ti-Al alloys.
  • the price of high-grade titanium raw materials has risen. Therefore, there is a growing need to obtain a high-quality, that is, low-oxygen Ti—Al alloy even when using titanium raw materials such as low-grade ores and scraps with a high oxygen content.
  • Patent Document 1 when PAM or CCIM is used and dissolved and held by adding 40% by mass or more of Al to high oxygen content Ti in an atmosphere of 1.33 Pa or higher, oxygen in the Ti—Al based alloy is reduced. combines with Al Al 2 in the form of O 3 is discharged from in Ti-Al deoxidation progresses, and that the addition of flux CaO-CaF 2 based, activity of Al 2 O 3 is reduced Further, it is described that deoxidation further proceeds.
  • low-grade Ti in other words, high-grade Ti such as pure Ti is added to a Ti—Al-based alloy in which Al 2 O 3 or CaO—CaF 2 -based flux is partially left. It is also described that if Al is diluted, a Ti—Al based alloy having an Al content of less than 40% by mass and a low oxygen content can be produced.
  • the Ti-Al-based alloy has parts which as Al 2 O 3 and flux remaining, melting it in Ti-Al alloy of the Al content by adding pure Ti is less than 40 wt%
  • Al 2 O 3 and the like inside the flux are decomposed / re-dissolved, and the oxygen concentration and the like are increased. Therefore, with the production method of Patent Document 1, it is not easy to obtain a high-quality, that is, low-oxygen Ti—Al-based alloy with an Al content of less than 40% by mass.
  • the portion where Al 2 O 3 or the like remains is mechanically removed by cutting or the like and then dissolved by adding high-grade, that is, low-oxygen Ti, the low oxygen content of less than 40% by mass is obtained.
  • a Ti-Al alloy can be obtained, but a part of the metal Ti is also removed at the time of mechanical removal of Al 2 O 3 etc., so the yield of the Ti-Al alloy becomes very poor. This leads to an increase in cost.
  • Patent Documents 2 to 5 disclose techniques useful for separating / removing substances such as residual flux from Ti—Al based alloys.
  • Patent Document 2 when an active metal is continuously melted and solidified to cast an ingot by using a plasma arc as a heat source, a flux such as CaF 2 is heated and melted in advance and then the active metal is charged. Alternatively, it is put together with the active metal, and a flux is contained between the water-cooled copper crucible and the ingot to slowly cool and solidify the surface of the ingot, thereby melting the ingot with a smooth ingot surface. Is described.
  • Patent Document 3 discloses a flux such as CaF 2 when casting an ingot by continuously melting and solidifying titanium or a titanium alloy using a plasma-cooled water-cooled copper mold with a plasma arc as a heat source. By changing the addition amount according to the mold position, the effect of slowly cooling the interface between the water-cooled copper mold and the molten metal is developed, and as a result, casting a slab with a good casting surface condition Is described as being possible.
  • a cold-crucible levitation and dissolution apparatus (CCIM) is used to add rare earth metal (cerium or misch metal in the examples) to Ti and calcium fluoride (CaF 2 ) as a flux to Ti.
  • rare earth metal cerium or misch metal in the examples
  • CaF 2 calcium fluoride
  • a molten flux can be present between the molten metal and the water-cooled copper crucible, and by transferring solid or liquid non-metallic inclusions to the molten flux layer, the molten metal improves the cleanliness of the molten metal.
  • a purification method is described.
  • non-metallic inclusions when a metal containing non-metallic inclusions is melted using a high-frequency induction furnace such as CCIM, the non-metallic inclusions have a lower electrical conductivity than metals such as Ti. It is known that there is a tendency to gather outside (water-cooled copper crucible side). Therefore, if the method of Patent Document 4 is used, non-metallic inclusions such as Al 2 O 3 may be localized and physically removed from the Ti—Al-based alloy.
  • Patent Document 5 discloses an induction melting furnace provided with a water-cooled copper crucible in which a crucible main body is movable in the vertical direction relative to the contents accommodated in the furnace. This Patent Document 5 also describes that a long active metal ingot is produced by repeatedly dissolving a metal raw material and lowering a water-cooled copper crucible. This Patent Document 5 is also similar to Patent Document 4 in that a high-frequency induction furnace equipped with a water-cooled copper crucible is used. In principle, non-metallic inclusions tend to gather outside the metal ingot. Therefore, there is a possibility that non-metallic inclusions such as Al 2 O 3 can be physically removed from the Ti—Al based alloy as in Patent Document 4.
  • Patent Document 2 Al 2 O 3 and CaO—CaF 2 flux remaining in the Ti—Al based alloy, which is a problem in Patent Document 1, can be mechanically removed on the ingot surface. Although it can be discharged, the method of Patent Document 2 uses a flux such as CaF 2 for the purpose of smoothing the cast surface of the ingot, and cannot be expected to have an effect of deoxidation or inclusion removal.
  • a plasma arc is used as a heat source, and high oxygen Ti, Al, and CaO—CaF 2 fluxes are continuously added to a bottomless water-cooled copper mold and melted downward. If withdrawn, the flux remains solid, or to coagulate migrate between the molten metal dissolves immediately after a water-cooled copper mold and Ti-Al alloy, it is dissolved Al 2 O 3 in the flux Al 2 O Solidification is performed before the activity of 3 is sufficiently reduced, and it is considered that the deoxidation promoting effect and inclusion removal effect due to the decrease in the activity of Al 2 O 3 can hardly be expected.
  • Patent Document 4 simply dissolves a metal containing non-metallic inclusions using a cold-crucible levitation and dissolution apparatus (CCIM), and a non-metal such as Al 2 O 3. It is not a suitable condition for inclusions to migrate into the flux. Therefore, even if the transition of non-metallic inclusions to the flux occurs, the possibility that a sufficient amount of transition is performed is low, and there is a high possibility that the non-metallic inclusions remain in the molten metal (described later). In the comparative example 1 and the comparative example 2 of the example according to the second embodiment, the result that the nonmetallic inclusion remains is actually obtained).
  • CCIM cold-crucible levitation and dissolution apparatus
  • Patent Document 4 does not describe how to treat the flux remaining in the molten metal. . In other words, if the flux remaining in the molten metal cannot be removed from the molten metal by any method, a Ti—Al alloy with high cleanliness cannot be obtained even using the technique of Patent Document 4.
  • the method for producing an active metal ingot of Patent Document 5 can in principle collect non-metallic inclusions on the outside of the metal ingot, as in Patent Document 4, but non-metallic inclusions. Since it is not a condition suitable for transferring to the flux, there is a possibility that non-metallic inclusions such as Al 2 O 3 in the Ti—Al alloy cannot be actually removed (second embodiment described later). In Comparative Example 3 of the example, a result in which nonmetallic inclusions remain is actually obtained).
  • Patent Document 5 does not assume dissolution with addition of flux, and there is no description regarding deoxidation and inclusion removal. Therefore, it is unclear whether deoxidation or inclusion removal can be performed without any problems when the pulling-down is performed at the pulling-down rate specified in Patent Document 5.
  • the speed at the time of lowering is set to 30 mm or less per minute.
  • the flux layer breaks and the molten metal leaks out, so that deoxidation is ensured. It may not be done.
  • the present invention has been made in view of the above-mentioned problems. From a low-grade titanium material containing a high concentration of oxygen, a high-grade and low-oxygen Ti—Al alloy is efficiently produced with a high yield. It is an object of the present invention to provide a method for producing a Ti—Al based alloy that can be produced.
  • the manufacturing method of the Ti—Al based alloy of the present invention takes the following technical means. That is, the method for producing a Ti—Al based alloy of the present invention is based on a Ti—Al based alloy comprising a titanium material and an aluminum material and containing a total of 0.1 mass% or more of oxygen and 40 mass% or more of Al. A dissolved raw material obtained by adding a CaO—CaF 2 -based flux in which 35 to 95% by mass of calcium fluoride is mixed with calcium oxide to 3 to 20% by mass with respect to the Ti—Al-based alloy is added to 1.33 Pa.
  • a primary ingot manufacturing process in which the primary ingot is melted by melting and holding by a melting method using a water-cooled copper container in the above atmosphere, and the primary ingot is bottomless in an atmosphere of 1.33 Pa or more
  • a secondary ingot manufacturing step for continuously drawing a secondary ingot while being melted by a melting method using a water-cooled copper mold, and a flux for mechanically removing the surface adhering flux layer of the secondary ingot A layer removal step, Characterized by (hereinafter sometimes referred to this embodiment the first embodiment).
  • Ti—Al based alloy production method of the present invention is a Ti—Al based alloy comprising a titanium material and an aluminum material and containing a total of 0.1 mass% or more of oxygen and 40 mass% or more of Al.
  • a melting raw material in which CaO—CaF 2 flux containing 35 to 95% by mass of calcium fluoride and calcium oxide is mixed to 3 to 20% by mass with respect to the Ti—Al alloy is cast.
  • the first divided body is charged into a bottomless water-cooled copper mold, dissolved in an inert gas atmosphere of 1.33 Pa or higher, and the bottom of the water-cooled copper mold is pulled down at a rate of 15 mm or less per minute.
  • the melted raw material second divided body divided in the raw material dividing step is charged into the water-cooled copper mold and dissolved in an inert gas atmosphere of 1.33 Pa or more, and the water-cooled copper mold is 15 mm or less per minute.
  • a titanium material is added to the ingot after the flux layer removing step and dissolved by a melting method using a water-cooled copper container in an atmosphere of about 1.33 Pa (hereinafter referred to as titanium material adding / dissolving step). Therefore, it is preferable to obtain a Ti—Al alloy having an Al content of less than 40% by mass.
  • the melting method using the water-cooled copper container in the primary ingot manufacturing process is any one of an arc melting method, a plasma arc melting method, and an induction melting method.
  • the melting method using a bottomless water-cooled copper mold in the secondary ingot manufacturing step and the divided body base ingot manufacturing step may use plasma arc or induction heating as a heat source.
  • a high quality and low oxygen Ti—Al based alloy is efficiently produced from a low quality titanium material containing a high concentration of oxygen with a high yield. can do.
  • FIG. 3 is a diagram showing a Ti—Al-based alloy manufacturing method according to the first embodiment of the present invention divided into processes.
  • FIG. 5 is a diagram schematically showing a Ti—Al-based alloy manufacturing method according to a second embodiment of the present invention, divided into processes. It is a figure which shows the SEM image of the cross section of the secondary ingot obtained by the manufacturing method of this invention.
  • the Ti—Al-based alloy manufacturing method of the present embodiment has three steps of a primary ingot manufacturing process to a flux layer removing process, preferably a primary ingot manufacturing process to a flux.
  • a titanium material addition / dissolution step is further performed to increase the oxygen content to less than 0.1% by mass from the Ti-Al alloy material W containing 0.1% by mass or more of oxygen.
  • a high-quality Ti—Al-based alloy Z is manufactured.
  • the alloy material W used in the manufacturing method of the Ti—Al-based alloy Z is a mixture of a titanium material and an aluminum material, and during the melting, deoxidation is caused by the action of aluminum contained in the aluminum material. It is to do. Further, in the manufacturing method of the present invention, CaO—CaF 2 flux ⁇ is further added to the alloy material W to promote deoxidation. According to such a production method of the present invention, from an alloy material W containing 0.1% by mass or more of oxygen, finally, a high-grade Ti—Al based alloy Z having less than 0.1% by mass of oxygen. Can be obtained.
  • an aluminum material is added to the titanium material, the Ti-Al alloy alloy material W is deoxidized, and the deoxidized alloy material is melted as the primary ingot X. It is a process.
  • the alloy material W described above contains oxygen (O) in a total amount of 0.1% by mass or more and aluminum (Al) in an amount of 40% by mass or more. That is, the titanium material constituting the alloy material W includes titanium oxide (TiO 2 ) such as low-quality and high-oxygen sponge titanium, scrap raw material, and rutile ore. The reason why low-grade titanium materials are used for the alloy material W is that these titanium materials are inexpensive and easy to procure.
  • the alloy material W described above has a total oxygen content of 0.1% by mass or more.
  • the total content of oxygen in the alloy material W is less than 0.1% by mass, the content of oxygen is small and deoxidation itself is not necessary.
  • 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 W is considered to be about 25% by mass.
  • the reason why the Ti—Al-based alloy containing 40% by mass or more of Al is used for the alloy material W to be deoxidized in the primary ingot manufacturing process is as follows.
  • the maximum amount of oxygen dissolved in a Ti—Al alloy is Ti—Al
  • the solid solution oxygen concentration tends to decrease.
  • the Al content in the alloy Z increases, the solid solution oxygen concentration tends to decrease.
  • the Al content is increased to 40% by mass or more, the alloy material W in the alloy material when deoxidation is performed.
  • the present inventors have completed the present invention, thinking that oxygen can be lowered.
  • the flux ⁇ described above has a function of reducing the activity of Al 2 O 3 in the alloy material W by being added to the alloy material W and promoting the deoxidation reaction. That is, the flux ⁇ dissolves Al 2 O 3 which is a deoxidation product of the Ti—Al alloy, thereby reducing the activity of Al 2 O 3 which is a generated species in the deoxidation reaction, and deoxidizing the flux ⁇ . Has the effect of promoting the reaction.
  • the content of CaF 2 in the flux ⁇ is set to 35% by mass or more so that the melting point of the flux ⁇ is 1800K or less.
  • Ti-Al alloy Z obtained as a product so as not to be contaminated with fluorine in CaF 2 the content of CaF 2 in the flux ⁇ is set to 95 wt% or less.
  • the amount of the CaO—CaF 2 -based flux ⁇ added to the alloy material W is 3% by mass to 20% by mass with respect to the Ti—Al-based alloy Z. If the amount added to the Ti—Al-based alloy Z is less than 3% by mass, the Al 2 O 3 activity is not significantly reduced, and the deoxidation promoting effect is hardly obtained. If the amount added to the Ti—Al-based alloy Z is more than 20% by mass, the risk that the added flux ⁇ remains in the manufactured Ti—Al-based alloy Z increases.
  • the atmosphere in which the deoxidation is performed does not necessarily have to be a high vacuum. That is, it is possible to sufficiently perform deoxidation even when dissolution is performed using a water-cooled copper container prepared in an atmosphere that is not a high vacuum atmosphere, specifically, an atmosphere of 1.33 Pa or higher. is there.
  • the loss of volatilization of Al or Ti as in the case of deoxidation in a high vacuum atmosphere is eliminated.
  • a low-oxygen Ti—Al alloy (high-grade Ti—) having a target composition is obtained while reducing the volatilization loss of Al and Ti (without substantially reducing the Ti content).
  • Al-based alloy can be easily manufactured.
  • the inside of the water-cooled copper container 1 is in an atmosphere of 1.33 Pa or more, more preferably 1.33 Pa to 5.33 ⁇ 10 5 Pa. It is carried out by adjusting to an atmosphere of ( ⁇ 5 atm).
  • agitation using a stirrer may be considered, but after the ingot is solidified in the container 1 (mold) as in the present embodiment, the top and bottom are inverted to pull the ingot.
  • the operation of repeating and re-dissolving may be performed a plurality of times.
  • the stirring operation by turning the ingot (primary ingot F) upside down can be performed more preferably 2 to 5 times. In this way, if the ingot is cast several times while reversing the top and bottom, the added flux ⁇ can be reliably mixed with the alloy material to promote the deoxidation reaction, and the deoxidation is sufficiently performed.
  • the primary ingot X can be melted.
  • the alloy material in the portion near the container wall of the water-cooled copper container 1 is not melted due to the effect of heat removal. Therefore, there is an undissolved (unreacted) portion in one dissolution, and a reaction for promoting deoxidation (deoxidation products Al 2 O 3 and CaO—CaF 2 flux ⁇ ) in the undissolved portion. Reaction) may not proceed sufficiently. Therefore, in the manufacturing method of the present embodiment, the operation of inverting the top of the primary ingot X and melting again is repeated a plurality of times.
  • the flux ⁇ is ingot (secondary ingot Y) so that Al 2 O 3 generated in the primary ingot manufacturing process is easily removed mechanically in the flux layer removing process described later.
  • the ingot in which the fluxes are biased in this way is the secondary ingot Y.
  • the primary ingot X is continuously drawn out downward while being melted by a melting method using a bottomless water-cooled copper mold 2 in an atmosphere of 1.33 Pa or higher.
  • the ingot Y is obtained.
  • a method of melting using a plasma arc or induction heating as a heat source can be used, but a method of melting using a plasma arc as a heat source is preferably used.
  • a flux ⁇ in which Al 2 O 3 is dissolved On the surface of the molten metal supplied to the inside of the water-cooled copper mold 2, a flux ⁇ in which Al 2 O 3 is dissolved floats. If a plasma arc is used as a heat source, the flux ⁇ is generated by the arc sprayed on the surface.
  • Coagulation is performed in a state of being concentrated in the vicinity of the inner peripheral surface and being concentrated in the vicinity.
  • the flux ⁇ is biased to exist on the outer peripheral side of the secondary ingot Y that is drawn downward.
  • the surface adhering flux layer ⁇ formed on the outer peripheral surface of the secondary ingot Y is shot blasted or ground in the flux layer removing process. If the mechanical means 3 is used, the Al 2 O 3 together with the flux can be removed.
  • the flux layer removing step is a step of scraping off the surface-adhered flux layer ⁇ formed on the outer peripheral surface of the secondary ingot in the secondary ingot manufacturing step by mechanical means 3 such as shot blasting or grinding. By performing this flux layer removal step, the oxygen concentration of the secondary ingot Y can be lowered as a whole.
  • the oxygen content contained in the Ti—Al based alloy Z is totaled by setting the Al content in the alloy material W to 40 mass% or more. Therefore, the Ti-Al alloy Z to be manufactured necessarily has an Al content of 40% by mass or more. However, when the obtained Ti—Al-based alloy Z is used, there is a desire to reduce the Al content to less than 40% by mass.
  • the titanium material addition / dissolution process described below may be performed.
  • the titanium material addition / dissolution step is performed by adding the titanium material V to the secondary ingot Y and dissolving it by a melting method using a water-cooled copper mold 4 (water-cooled copper container) in an atmosphere of 1.33 Pa or more.
  • a Ti—Al based alloy Z2 having an Al content of less than 40% by mass is obtained.
  • the melting method shown in the figure uses a water-cooled copper container, but the melting method used in this titanium material addition / dissolution step is a melting method other than water-cooled copper induction melting (CCIM), such as a vacuum arc melting method. (VAR) or vacuum induction melting (VIM) may be used.
  • CCIM water-cooled copper induction melting
  • VAR vacuum arc melting method
  • VIM vacuum induction melting
  • the titanium material V added to the secondary ingot Y in the titanium material addition / melting step is a Ti-Al alloy Z2 having an Al content of less than 40% by mass after the titanium material addition / melting step.
  • the Al content is preferably less than 40% by mass.
  • a titanium material V having an Al content of less than 40% by mass such as pure Ti that does not contain aluminum as an impurity, is added, the Al content contained in the secondary ingot Y is reduced by dilution.
  • a Ti—Al-based alloy Z2 whose amount is less than 40% by mass can be obtained.
  • the titanium material V added in the titanium material addition / dissolution process varies depending on the required quality of the Ti—Al alloy Z2 to be manufactured, components other than aluminum in the titanium material V (Sn, V, Mn The concentration of such metals other than aluminum cannot be specified.
  • the titanium material addition / dissolution process is performed in addition to the primary ingot manufacturing process to the flux layer removal process described above, a Ti-Al alloy Z2 that meets the required quality can be obtained for the composition other than oxygen and aluminum.
  • the convenience of the production method of the present invention can be further enhanced.
  • the manufacturing method of the Ti—Al-based alloy 101 has three steps of a raw material dividing step to a flux layer removing step, preferably after the raw material dividing step to the flux layer removing step. Further, a titanium material addition / dissolution step is performed to obtain a high-grade Ti—Al in which the oxygen content is less than 0.1% by mass from the alloy material of the Ti—Al alloy 101 containing 0.1% by mass or more of oxygen.
  • the system alloy 101 is manufactured.
  • the alloy material used in the manufacturing method of the Ti—Al alloy 101 is a mixture of a titanium material and an aluminum material.
  • the melting raw material 102 mixed with aluminum is melted in the divided body base ingot manufacturing process in this way, the aluminum reacts with oxygen in the alloy material to perform deoxidation.
  • CaO—CaF 2 -based flux 103 is added to the alloy material for the purpose of promoting deoxidation in the raw material dividing step.
  • a flux 103 is added in the raw material dividing step, deoxidation in the divided base ingot manufacturing step is further promoted, and oxygen is finally reduced from an alloy material containing 0.1% by mass or more of oxygen. It is possible to obtain a high-grade Ti—Al-based alloy 101 of less than 1 mass%.
  • the melted raw material 102 to which the flux 103 is added is divided into a plurality of pieces to form divided bodies.
  • the lowering operation is performed on all the divided bodies following the melting operation of the divided body of the melting raw material 102, and non-metallic inclusions such as Al 2 O 3 are added to the flux 103.
  • the flux 103 to which the non-metallic inclusions are transferred can be unevenly distributed (localized) on the outer peripheral surface of the ingot.
  • the non-metallic inclusions and the flux 103 that are unevenly distributed in this way are mechanically removed in the flux layer removing step, or preferably the component adjustment is further performed in the titanium material adding / dissolving step, so that the Ti—Al of the present invention A system alloy 101 is manufactured.
  • the flux 103 is added to the alloy material of the Ti—Al-based alloy 101 to produce the molten raw material 102, the produced molten raw material 102 is divided into n pieces, and the first divided body 141 ⁇ The n-th divided body is formed.
  • This dividing operation of the melting raw material 102 is a feature of the manufacturing method of the present invention.
  • the alloy material of the Ti—Al based alloy 101 used for the melting raw material 102 is made of a titanium material and an aluminum material, and the total amount of oxygen is 0.1 mass% or more and Al is 40 mass%. Contains above.
  • the flux 103 blended in the alloy material is a CaO—CaF 2 -based flux 103 in which 35 to 95 mass% of calcium fluoride is blended with calcium oxide. The alloy material described above is blended with the flux 103 in an amount of 3 to 20% by mass to form the melting raw material 102 of this embodiment.
  • the titanium material constituting the above-mentioned alloy material is one containing a sponge titanium containing much oxygen in low-grade scrap material, titanium oxide such as rutile ore (TiO 2).
  • titanium oxide such as rutile ore (TiO 2).
  • the above-described alloy material has a total oxygen content of 0.1% by mass or more.
  • the total content of oxygen in the alloy material is less than 0.1% by mass, the content of oxygen is small and deoxidation itself is not necessary.
  • 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% by mass.
  • the reason why the Ti—Al alloy 101 containing 40% by mass or more of Al is used as the alloy material used for the melting raw material 102 in the raw material dividing step is based on the following reason.
  • the maximum amount of oxygen dissolved in the Ti—Al alloy 101 is Ti—
  • the Al content in the Al-based alloy 101 is increased, the dissolved oxygen concentration tends to decrease.
  • the melting raw material 102 containing the Ti—Al alloy 101 produced using a low-grade titanium material can be removed in the divided base ingot manufacturing process if the Al content is increased to 40% by mass or more.
  • the inventors have thought that oxygen in the alloy material can be lowered when acid is performed, and the present inventors have completed the present invention.
  • the flux 103 described above has the function of reducing the activity of Al 2 O 3 in the melting raw material 102 by being added to the melting raw material 102 and promoting the deoxidation reaction in the divided body ingot manufacturing process described later. is doing. That is, the flux 103 dissolves Al 2 O 3 which is a deoxidation product of the Ti—Al-based alloy 101, thereby reducing the activity of Al 2 O 3 which is a generated species in the deoxidation reaction. Has the effect of promoting acid reaction.
  • the dissolution of Al 2 O 3 in the flux 103 occurs only when the flux 3 is melted. Therefore, if the melting point of the flux 103 becomes too high, the flux 103 does not melt and Al 2 O 3 does not dissolve. That is, in the case of the CaO—CaF 2 based flux 103, it is necessary to decrease the melting point of the flux 103 itself by increasing the content of CaF 2 having a low melting point. Specifically, in the deoxidation of the present embodiment, the content of CaF 2 in the flux 103 is set to 35% by mass or more so that the melting point of the flux 103 is 1800K or less.
  • the content of CaF 2 in the flux 103 It is 95 mass% or less.
  • the addition amount of the CaO—CaF 2 -based flux 103 to the melting raw material 102 is 3% by mass to 20% by mass with respect to the Ti—Al-based alloy 101 as a product. If the addition amount relative to Ti-Al alloy 101 is less than 3 wt%, Al 2 O 3 does not occur reduction in the activity of so much, no deoxidation promoting effect is hardly obtained. If the amount added to the Ti—Al based alloy 101 is more than 20 mass%, the risk that the added flux 103 remains in the manufactured Ti—Al based alloy 101 increases.
  • the melting raw material 102 is first prepared by blending the flux 103 with the alloy material.
  • the melting raw material 102 in which the flux 103 is mixed with the alloy material of the Ti—Al alloy 101 in the above-described raw material dividing step is charged into the water-cooled copper crucible 105 and melted (the solidification method in the crucible is performed).
  • Non-metallic inclusions such as Al 2 O 3 cannot be sufficiently removed. In order to sufficiently remove the non-metallic inclusions, it is necessary to perform an operation of a divided body base ingot manufacturing process as described below.
  • the prepared dissolving raw material 102 is divided into n pieces to form the first divided body 141 to the n-th divided body.
  • N which is the number of divisions of the melting raw material 102, is an integer of 2 or more, and the melting raw material 102 is divided into a plurality of divided bodies in the raw material dividing step.
  • the weight of each divided body is the maximum with respect to the final target ingot weight at the end of casting.
  • the melted raw material 2 after adjustment is divided into n so as to be 4/5 or less.
  • the divided body is preferably equally divided (in this case, 33.3 ton), but the present invention is not limited to equally dividing the divided body.
  • none of the first divided body 141 to the n-th divided body obtained in the raw material dividing step will exceed 4/5 of the final target ingot weight at the end of casting. Heat removal from the bottom 107 of the copper crucible 105 can be suppressed, and the deoxidation reaction can be sufficiently promoted.
  • the raw material weight of each divided body after dividing the molten raw material 102 is divided so as to be 4/5 or less of the whole at the maximum with respect to the final ingot weight. That is, at least two melting operations and two lowering operations (partition body charging / dissolution ⁇ lowering ⁇ partition body charging / dissolution ⁇ lowering) are required. This is because the portion close to the water-cooled copper crucible 105 at the bottom 107 is strongly cooled by only one melting operation, and solidification proceeds before the charged flux 103 is sufficiently melted. Therefore, Al 2 O 3 It is difficult for non-metallic inclusions such as these to react with the flux 103. In this regard, since the heat removal from the bottom 107 is suppressed in the second and subsequent melting operations, the flux 103 and the non-metallic inclusions sufficiently react with each other during the second and subsequent melting, thereby promoting deoxidation. To do.
  • the separation efficiency between the metal and the flux 103 can be lowered even if the second and subsequent melting operations are performed.
  • the weight of the first divided body 141 exceeds 4/5 of the final target weight, the non-metallic inclusions and the flux can be dissolved even if the amount less than the remaining 1 / V is dissolved in the second and subsequent dissolutions. Reaction with 103 is less likely to occur. For this reason, it is desirable to divide the divided body into a maximum of 4/5 or less, preferably 2/3 or less of the whole, more preferably I / 2 or less of the whole.
  • the present invention has been described by giving an example in which the dissolved raw material 102 is divided into three parts and deoxidized in the raw material dividing step, but the number of divisions is five. Even if it is 11 divisions, there is no problem.
  • the first divided body 141 of the melted raw material 102 divided in the raw material dividing process is charged into a water-cooled copper crucible 105 (bottomed water-cooled copper crucible 105) to be inactive at 1.33 Pa or more.
  • An operation of melting under a gas atmosphere and pulling down the water-cooled copper crucible 105 at a speed of 15 mm or less per minute is performed, and then the second divided body 142 of the melted raw material 102 divided in the raw material dividing step is bottomed out.
  • the ingot is formed by repeating.
  • the divided body base ingot manufacturing process includes a melting operation in which a divided body of the melting raw material 102 is charged into a water-cooled copper crucible 105 and melted in an inert gas atmosphere of 1.33 Pa or more, and this melting operation is followed. Then, the operation of continuously lowering the water-cooled copper crucible 105 downward at a speed of 15 mm / min or less is performed as “basic operation”. And this basic operation is performed once in order about each of the 1st division body 141, the 2nd division body 142, ..., and the nth division body.
  • the reason why the inert gas atmosphere is 1.33 Pa or more is that no volatilization loss of Al or Ti occurs as in the case of melting in a high vacuum atmosphere. More preferably, it is dissolved in an inert gas atmosphere of 1.33 Pa to 5.33 ⁇ 10 5 Pa ( ⁇ 5 atm).
  • the divided body base ingot manufacturing process proceeds by processing the melting raw material 102 in the order of the lowering operation of the divided body 142, the melting operation of the third divided body 143, and the lowering operation of the third divided body 143.
  • each divided body of the melting raw material 102 is charged into a water-cooled copper crucible 105 (water-cooled copper mold) prepared in an inert gas atmosphere of 1.33 Pa or more, and water-cooled.
  • the ingot is cast by melting each divided body of the melting raw material 102 in the copper crucible 105 using a plasma arc or induction heating as a heat source.
  • the melting is preferably performed using induction heating as a heat source.
  • the non-metallic inclusions gather outside the molten metal due to the difference in electrical conductivity between the non-metallic inclusions and the metal. It is known. That is, the flux 103 in which the Al 2 O 3 in the molten metal supplied into the water-cooled copper crucible 105 is concentrated in the vicinity of the inner peripheral surface of the mold due to induction heating, and solidification is performed in the state of being concentrated. As a result, the surface-attached flux layer 108 in which the flux 103 is biased and present on the outer peripheral side of the ingot drawn downward is formed in the ingot melted in the divided body base ingot manufacturing process.
  • the surface-attached flux layer 108 can be scraped off by mechanical means such as shot blasting or grinding in the flux layer removing process. This is because non-metallic inclusions such as Al 2 O 3 can be removed.
  • the pulling-down operation performed following the melting operation of the divided body of the melting raw material 102 in the divided body base ingot manufacturing process is the surface adhesion formed on the surface of the ingot by melting the flux 103 by the above-described melting operation.
  • the flux layer 108 is unevenly distributed between the mold and the ingot.
  • the above-described water-cooled copper crucible 105 has a structure in which a cylindrical crucible body 106 that opens both upward and downward and a bottom portion 107 that is disposed on the bottom side of the crucible body 106 are combined. It has become.
  • the bottom 107 of the water-cooled copper crucible 105 is attached to the crucible main body 106 so as to be movable in the vertical direction.
  • the cast placed on the upper side of the bottom 107 is performed.
  • the lump can also be lowered.
  • the surface adhering flux layer 108 is unevenly distributed between the outer periphery side of the ingot, in other words, between the mold and the ingot.
  • the ingot lowering speed in other words, the lowering speed of the bottom 107 of the water-cooled copper crucible 105 is set to 15 mm / min or less, preferably 10 mm / min or less. If the ingot lowering speed exceeds 15 mm / min, the surface-adhered flux layer 108 formed on the outer peripheral surface of the ingot in the above-described divided body base ingot manufacturing process is broken, and the surface-adhered flux layer 108 is used as a mold. This is because it is difficult to make it unevenly distributed between the steel and the ingot.
  • the one that performs the above-described dissolving operation and pulling-down operation once at a time is the “basic operation” for a certain divided body. This “basic operation” is performed once for each of the first divided body 141, the second divided body 142,.
  • the melting raw material 102 is divided into three, and the first divided body 141, the second divided body 142, and the third divided body 143 exist, Melting operation of first divided body 141 ⁇ Lowering operation of first divided body 141 ⁇ Melting operation of second divided body 142 ⁇ Lowering operation of second divided body 142 ⁇ Melting operation of third divided body 143 ⁇ Third divided body 143 In the end, a cylindrical ingot that is long in the vertical direction is melted (cast) in the divided base ingot manufacturing process.
  • the outer peripheral surface of the ingot was cast with the above-mentioned divided body based ingot manufacturing process and surface deposition flux layer 108 solidified in a state where the flux 103 is biased is formed on the surface adhering flux layer 108 Al 2
  • Non-metallic inclusions such as O 3 are also contained at a high concentration. Therefore, if the surface adhering flux layer 108 formed on the outer peripheral surface of the ingot is scraped by mechanical means such as shot blasting or grinding in the flux layer removing step, the non-metallic inclusions such as Al 2 O 3 together with the flux 103 The oxygen concentration contained in the ingot can be lowered as a whole.
  • the Ti—Al-based alloy 101 obtained from the raw material dividing step through the flux layer removing step has the surface-attached flux layer 108 formed on the outer peripheral surface of the ingot in the divided body base ingot manufacturing step. Since it is removed by mechanical means such as shot blasting and grinding in the process, the oxygen content contained in the Ti-Al alloy 101 is greatly reduced, and the oxygen originally contained in the alloy material is reliably deoxidized. Has been reduced. That is, according to the manufacturing method of the Ti—Al based alloy 101 of the present embodiment, the high quality, that is, the low oxygen Ti—Al based alloy 101 is efficiently produced from the low quality titanium containing a high concentration of oxygen with a high yield. Can be manufactured.
  • the oxygen content contained in the Ti—Al based alloy 101 is totaled by setting the Al content in the alloy material to 40% by mass or more. Since the Ti content is less than 0.1% by mass, the produced Ti—Al-based alloy 101 inevitably has an Al content of 40% by mass or more. However, when the obtained Ti—Al-based alloy 101 is used, there is a desire to reduce the Al content to less than 40% by mass.
  • the titanium material addition / dissolution step described below may be performed.
  • the titanium content is added to the ingot and melted by a melting method using a water-cooled copper mold (water-cooled copper container 109) in an atmosphere of 1.33 Pa or higher, so that the Al content is increased.
  • a Ti—Al alloy 101 of less than 40% by mass is obtained.
  • the melting method illustrated in FIG. 2 uses a water-cooled copper container, but the melting method used in this titanium material addition / dissolution step is a melting method other than water-cooled copper induction melting (CCIM), such as a vacuum arc.
  • CCIM water-cooled copper induction melting
  • VAR vacuum induction melting
  • VIM vacuum induction melting
  • the titanium material added to the ingot in the titanium material addition / melting step is to obtain a Ti—Al alloy 101 having an Al content of less than 40 mass% after the titanium material addition / melting step.
  • the titanium content is preferably less than 40% by mass.
  • a titanium material with an Al content of less than 40% by mass such as pure Ti that does not contain aluminum as an impurity, is added, the Al content contained in the ingot is reduced by dilution, so the Al content is 40% by mass.
  • a Ti—Al alloy 101 that is less than 1% can be obtained.
  • the titanium material added in the titanium material addition / dissolution step varies depending on the required quality of the Ti—Al alloy 101 to be manufactured. Therefore, components other than aluminum (such as Sn, V, Mn, etc.) in the titanium material. The concentration of the metal other than aluminum cannot be specified and can be arbitrarily changed.
  • the ratio (H / D) between the final ingot height H (final target ingot height) and the ingot diameter D is not particularly limited. From the viewpoint, it is preferably 1 or more.
  • the Ti—Al alloy 101 that matches the required quality can be obtained for the composition other than oxygen and aluminum. The convenience of the manufacturing method can be further enhanced.
  • Example 1 the alloy material W containing 40% by mass of Al and 0.8% by mass of O was processed from the primary ingot manufacturing process to the titanium material adding / dissolving process. Is an alloy material W containing 50% by mass of Al and 0.8% by mass of O as compared with Example 1 and subjected to the treatment from the primary ingot manufacturing process to the titanium material addition / dissolution process. is there.
  • the comparative example 1 and the comparative example 2 do not perform a secondary ingot manufacturing process and a flux layer removal process after a primary ingot manufacturing process among four processes which comprise the manufacturing method of this invention, The titanium material is directly added and dissolved.
  • Comparative Example 1 the inclusions that were confirmed to be generated after the primary ingot manufacturing step were left without being removed, and Comparative Example 2 was obtained by removing inclusions as much as possible.
  • the primary ingot manufacturing process scrap Ti, titanium oxide (TiO 2), pure Al, the CaO-CaF 2 as a raw material by a plasma arc melting method, intermediate material (Ti-40, 50 wt% Al-0 .8 mass% O), the secondary ingot manufacturing step, the ingot manufactured in the primary ingot manufacturing step is remelted by the plasma arc drawing melting method, and the flux layer removing step is The step of mechanically removing the flux layer (containing Al 2 O 3 ) adhering to the ingot surface after the secondary ingot manufacturing step and the titanium material addition / dissolution step are the primary ingot manufacturing step (Comparative Example 1).
  • Comparative Example 2 Ti—Al ingot produced in the primary ingot production process + secondary ingot production process + flux layer removal process (Examples 1 and 2), pure Ti (O: 0.
  • a plasma arc melting method A step of melting the -30 wt% Al ingot.
  • TiO 2 titanium oxide
  • Comparative Example 1 a Ti-Al alloy is melted by directly adding and melting a titanium material after the primary ingot manufacturing process. That is, in Comparative Example 1, the primary ingot is not subjected to the secondary ingot manufacturing process in which the primary ingot is continuously drawn while being melted by a melting method using a bottomless water-cooled copper mold. internal and remains from entrapment as Al 2 O 3 or flux, not performed the flux layer removing step.
  • the oxygen concentration was measured by the inert gas melting method for both the portion where the inclusion was confirmed and the portion where the inclusion was not confirmed, the inclusion was confirmed as shown in Table 1. At the position where the oxygen concentration was 1.82% by mass, and at the position where no inclusion was confirmed, the oxygen concentration was 0.24% by mass. From this, it can be seen that the inclusions confirmed by SEM observation are inclusions such as flux and Al 2 O 3 .
  • a titanium material (pure Ti) containing 0.05% by mass of oxygen is added to the ingot after the primary ingot manufacturing process, so that the Al content becomes 30% by mass.
  • a Ti—Al alloy having an oxygen concentration of 0.79% by mass was obtained.
  • Comparative Example 1 pure Ti (0.05% by mass of O is contained in the titanium material addition / dissolution step with respect to the alloy material in which oxide inclusions remain after the flux layer removal step.
  • oxides such as Al 2 O 3 are decomposed and redissolved in the molten metal, and the oxygen concentration is increased.
  • Comparative Example 2 In contrast to Comparative Example 1 described above, Comparative Example 2 is obtained by mechanically removing the Ti—Al alloy region containing oxide inclusions that was confirmed after the primary ingot manufacturing process. That is, since oxygen is removed from the Ti—Al based alloy by removing inclusions, the oxygen content of Comparative Example 2 is comparative when the Al content is 30% by mass. The oxygen content is 0.21% by mass, which is smaller than in Example 1. However, when removing the oxide inclusions, not only the inclusions contained in the ingot but also the metal (Ti—Al alloy) is lost. Therefore, the “intermediate material use amount” indicating how much of the alloy material has become a Ti—Al alloy, in other words, “yield” is 50%, which is about half of Comparative Example 1. Yes.
  • Example 1 In contrast to Comparative Example 1 and Comparative Example 2 described above, Example 1 is prepared by mixing the same raw materials as Comparative Example 1 and Comparative Example 2 to adjust the alloy material W, and further adding CaO—CaF 2 flux to the alloy material W.
  • the processing conditions for melting the primary ingot X are also the same as in the comparative example, using a 100 kW plasma arc furnace and melting at a pressure of 1.20 ⁇ 10 5 Pa.
  • Example 1 differs from the comparative example in that the upside down and remelting, which was not the comparative example, is repeated three times.
  • the secondary ingot Y is melted while being drawn downward by a melting method using a plasma arc as a heat source. did.
  • CaO—CaF 2 -based flux ⁇ containing Al 2 O 3 was discharged and adhered to the surface of the secondary ingot Y.
  • the secondary ingot Y was subjected to shot blasting (mechanical means 3) in the flux layer removing step to remove the flux layer ⁇ on the surface of the secondary ingot Y.
  • pure Ti oxygen concentration 0.05 mass% is further added as a titanium material addition / dissolution step, and Ti-30 mass% Al alloy Z2 is melted to reduce the oxygen concentration. analyzed.
  • Example 2 In addition, the knowledge as obtained in Example 1 described above can also be obtained for the alloy material W of Example 2 in which the Al content is 50 mass% higher than in Example 1.
  • CaO—CaF 2 flux 103 is added to an alloy material prepared by mixing an aluminum material with a titanium material to deoxidize O (oxygen) contained in the alloy material. It is a thing.
  • Example 1 the alloy material containing 40% by mass of Al and 0.8% by mass of O was processed from the raw material dividing step to the titanium material adding / dissolving step.
  • Example 2 the alloy material containing 60% by mass of Al and 0.8% by mass of O was processed from the raw material dividing step to the titanium material adding / dissolving step.
  • Example 3 the alloy material containing 45% by mass of Al and 0.8% by mass of O was subjected to the raw material dividing step to the titanium material adding / dissolving step.
  • Example 4 the alloy material containing 52% by mass of Al and 0.8% by mass of O is subjected to the raw material dividing step to the titanium material adding / dissolving step.
  • the number of divisions of the melting raw material 2 in Examples 1 to 4 is “11”, and one melting operation and one time are performed for each of the first divided body 141 to the eleventh divided body (not shown).
  • the "basic operation” consists of a pull-down operation.
  • Comparative Example 1 uses an alloy material having the same composition as Example 1, but the melting raw material 102 is not divided during the raw material dividing step, and only the melting operation is performed in the divided body base ingot manufacturing step. The ingot is obtained by performing. In Comparative Example 1, the obtained ingot was further subjected to a titanium material addition / dissolution step to obtain a Ti-30Al ingot.
  • Comparative Example 2 was obtained by performing the same process as Comparative Example 1 to obtain an ingot, and the titanium material addition / dissolution step was performed using only a specific part of the obtained ingot.
  • Comparative Example 3 As in Example 1, the alloy material containing 40% by mass of Al and 0.8% by mass of O was processed from the raw material dividing step to the titanium material adding / dissolving step. . Comparative Example 3 is different from Example 1 in that the flux 103 is not blended with the melting raw material 102.
  • scrap Ti, titanium oxide (TiO 2 ), and pure Al are used as alloy materials.
  • a CaO—CaF 2 flux 103 is used as a Ti—Al system. 10% of the weight of the alloy 101 was blended, and in Comparative Example 3, the melting raw material 102 was produced without blending the flux 103.
  • the melted raw material 102 prepared in the raw material splitting process is charged into a water-cooled copper crucible 105 (inner diameter 80 mm) having no bottom, and argon as an inert gas is introduced. It melt
  • the melting raw material 102 is divided into 11 parts in the raw material dividing process, and the first divided body 141 to the 11th divided body (not shown) are preliminarily formed.
  • the dissolution operation and the pull-down operation were performed once for each of the divided bodies, and the dissolution raw material 102 was dissolved to proceed with deoxidation. Moreover, about the comparative example 1 and the comparative example 2, as above-mentioned, the division body base ingot manufacturing process itself is not implemented.
  • the surface-attached flux layer adhered to the surface of the ingot by performing shot blasting as a mechanical means on the surface of the ingot with respect to the ingot cast in the divided body base ingot manufacturing step 108 was removed.
  • the oxygen concentration contained in the ingot was analyzed by an inert gas melting method.
  • pure Ti having an oxygen concentration of 0.05 mass% is added to the ingot from which the surface adhering flux layer 108 has been removed in the flux layer removing step using a plasma arc melting furnace.
  • Ti-30 mass% Al alloy was melted.
  • the oxygen concentration was analyzed by an inert gas melting method in the same manner as the ingot after the flux layer removal step.
  • Table 2 shows the analysis results of Examples and Comparative Examples.
  • Comparative Example 1 In Comparative Example 1, as described above, the melting raw material 102 is not divided in the raw material dividing step, and only the melting operation without the pulling-down operation is performed on the molten raw material 102 that is not divided in the divided body base ingot manufacturing process. Thus, an ingot is obtained.
  • oxygen was 0.50% by mass in a site where no inclusion was present, and in a site where an inclusion was present 1.16% by mass of oxygen was detected.
  • the ingot described above is melted using a plasma arc melting furnace in the titanium material addition / melting step, and pure Ti (oxygen concentration 0.05 mass%) is added to the ingot to obtain a Ti-30 mass% Al alloy.
  • the oxygen concentration of the resulting Ti-30 mass% Al alloy ingot was analyzed by an inert gas melting method. As a result of the analysis, 0.79% by mass of oxygen was detected. Furthermore, when the inside of an ingot of Ti-30 mass% Al alloy was observed with an SEM, the presence of oxide inclusions such as Al 2 O 3 was not confirmed.
  • the oxygen concentration increased from 0.50% by mass to 0.79% by mass in the portion where no inclusion was present. This is because, when pure Ti110 is added to the ingot in the titanium material addition / melting step and the components are adjusted, the oxide inclusions remaining in the ingot are decomposed by pure Ti and become Ti-Al. It is considered that the oxygen concentration has increased due to re-dissolution.
  • Comparative Example 2 In Comparative Example 2, the ingot is melted by the same melting raw material 102 and melting method as in Comparative Example 1. Therefore, the oxygen concentration of the site where the melted ingot inclusions are not present is 0.51% by mass, and the site where the inclusions are present is 1.12% by mass. Of the ingot of Comparative Example 2, a portion where no inclusions were present was selected and melted using a plasma arc melting furnace, and pure Ti110 (oxygen concentration 0.05 mass%) was added to obtain Ti-30. An ingot of mass% Al alloy was melted. As a result of analyzing the oxygen concentration of the molten ingot, the oxygen concentration was 0.42% by mass, which was lower than that of Comparative Example 1.
  • Comparative Example 3 In the same manner as in Comparative Example 1 and Comparative Example 2, the melting raw material 102 was prepared so as to be Ti-40 mass% Al-0.8 mass% O, and an ingot (2800 g) was melted. Unlike the comparative example 1 and the comparative example 2, the melting raw material 102 of the comparative example 3 was prepared by dissolving the raw material 102 without adding the flux 103 to the alloy material in the raw material dividing step. It is divided into 11 pieces. Specifically, the first divided body 141 initially charged in the water-cooled copper crucible 105 has a raw material weight of 800 g (excluding the flux 103), and thereafter the second divided body 142 to the eleventh divided portion to be additionally charged. The body 151 has a raw material weight of 200 g.
  • the raw material (800 g) of the first divided body 141 was charged on a starting block made of pure Ti (the bottom 107 of the water-cooled copper crucible 105), and the pressure was 6.6 ⁇ 10 4 Pa in an Ar atmosphere. Dissolved in the crucible. After the 1st division body 141 melt
  • Example 1 In Example 1, as in Comparative Example 3, the melting raw material 102 was divided into 11 pieces and the ingot was melted. The difference between Example 1 and Comparative Example 3 is that 10% by mass of the flux 103 is blended with respect to the weight of the Ti—Al alloy 101.
  • the flux layer on the surface of the ingot could be easily removed by shot blasting.
  • the oxygen concentration in the portion where Al 2 O 3 does not exist is 0.30% by mass. Even at a site where oxide inclusions such as Al 2 O 3 were slightly observed, the oxygen concentration was as very low as 0.40% by mass. Therefore, in Example 1 in which the flux 103 was blended in the raw material dividing step and the melting raw material 102 was divided, and the melting operation and the lowering operation were repeated for each divided body in the divided body base ingot manufacturing step. It can be seen that the oxygen concentration inside can be greatly reduced.
  • Example 2 In Example 2, as in Comparative Example 3, the melting raw material 102 was divided into 11 pieces and the ingot was melted. The difference between Example 2 and Comparative Example 3 is that 10% by mass of the flux 103 is blended with respect to the weight of the Ti—Al-based alloy 101.
  • the flux layer on the surface of the ingot could be easily removed by shot blasting.
  • the oxygen concentration of the portion where Al 2 O 3 does not exist is 0.045% by mass. Even at a site where oxide inclusions such as Al 2 O 3 were slightly observed, the oxygen concentration was as very low as 0.065% by mass. Therefore, in Example 2 in which the flux 103 was blended in the raw material dividing step and the melting raw material 102 was divided, and the melting operation and the lowering operation were repeated for each divided body in the divided body base ingot manufacturing step. It can be seen that the oxygen concentration inside can be greatly reduced.
  • the oxide material inclusions in the ingot were hardly present in the titanium material addition / dissolution step of Example 2, so that even when remelted, oxygen It was found that the concentration did not increase and there was no yield reduction. Therefore, by using the production method of the present invention, it is possible to efficiently produce a low-oxygen Ti—Al-based alloy 101 having an Al content of less than 60 mass% with a high yield using low-grade raw materials. It is judged that.
  • Example 3 In Example 3, as in Comparative Example 3, the melting raw material 102 was divided into 11 pieces and the ingot was melted. Example 3 is different from Comparative Example 3 in that the flux 103 is blended by 10 mass% with respect to the weight of the Ti—Al alloy 101.
  • the flux layer on the surface of the ingot (surface-adhered flux layer 108) could be easily removed by shot blasting.
  • the oxygen concentration in the portion where Al 2 O 3 does not exist is 0.16% by mass. Even at a site where oxide inclusions such as Al 2 O 3 were slightly observed, the oxygen concentration was as low as 0.20% by mass. Therefore, in Example 3 in which the flux 103 was blended in the raw material dividing step and the melting raw material 102 was divided, and the melting operation and the lowering operation were repeatedly performed for each divided body in the divided body base ingot manufacturing step. It can be seen that the oxygen concentration inside can be greatly reduced.
  • Example 4 In Example 4, as in Comparative Example 3, the melting raw material 102 was divided into 11 pieces and the ingot was melted. The difference between Example 4 and Comparative Example 3 is that 10% by mass of the flux 103 is blended with respect to the weight of the Ti—Al-based alloy 101.
  • the flux layer on the surface of the ingot could be easily removed by shot blasting.
  • the oxygen concentration in the portion where Al 2 O 3 does not exist is 0.042% by mass. Even at a site where oxide inclusions such as Al 2 O 3 were slightly confirmed, the oxygen concentration was as very low as 0.060% by mass.
  • Example 4 where the flux 103 was blended in the raw material dividing step and the melting raw material 102 was divided, and the melting operation and the lowering operation were repeated for each divided body in the divided body base ingot manufacturing step, the ingot It can be seen that the oxygen concentration inside can be greatly reduced.
  • embodiment disclosed this time is an illustration and restrictive at no points.
  • matters that are not explicitly disclosed, for example, operating conditions and operating conditions, various parameters, dimensions, weights, volumes, and the like of a component deviate from a range that a person skilled in the art normally performs. Instead, values that can be easily assumed by those skilled in the art are employed.
  • Japanese Patent Application No. 2017-032273 Japanese patent application filed on April 13, 2017
  • Japanese Patent Application No. 2017-079928 Japanese patent application filed on October 11, 2017. This is based on a Japanese patent application (Japanese Patent Application No. 2017-197905), the contents of which are incorporated herein by reference.
  • a high-grade and low-oxygen Ti—Al alloy can be efficiently produced from a low-grade titanium material containing oxygen at a high concentration with a high yield, and it is a material for aircraft and automobiles. It is particularly useful in the production of

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Abstract

La présente invention comprend : une étape de production de lingot primaire dans laquelle de 3 à 20 % en masse d'un flux de CaO-CaF2 obtenu par mélange de 35 à 95 % en masse de fluorure de calcium avec de l'oxyde de calcium, sont ajoutés à un matériau d'alliage de Ti-Al comprenant un total d'au moins 0,1 % en masse d'oxygène, et au moins 40 % en masse d'Al, et la substance résultante est fondue au moyen d'un procédé de fusion à l'aide d'un récipient en cuivre refroidi avec de l'eau sous une atmosphère ayant une pression de 1,33 Pa ou plus, et maintenue, pour produire un lingot primaire ; une étape de production de lingot secondaire dans laquelle le lingot primaire est étiré en continu vers le bas tout en étant fondu au moyen d'un procédé de fusion à l'aide d'un moule de coulée en cuivre refroidi avec de l'eau sans fond sous une atmosphère ayant une pression de 1,33 Pa ou plus, pour obtenir un lingot secondaire Y ; et une étape de retrait de la couche de flux dans laquelle une couche de flux déposée sur la surface du lingot secondaire Y est retirée mécaniquement.
PCT/JP2018/006823 2017-02-23 2018-02-23 Procédé de production d'alliage de ti-al WO2018155658A1 (fr)

Priority Applications (2)

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EP18756604.7A EP3586998B1 (fr) 2017-02-23 2018-02-23 Procédé de production d'alliage de ti-al
US16/487,182 US11377714B2 (en) 2017-02-23 2018-02-23 Method for producing Ti-Al alloy

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110629180A (zh) * 2019-10-16 2019-12-31 河北冠靶科技有限公司 一种应用于靶材的大尺寸无氧铜锭的生产装置及方法
CN113684456A (zh) * 2021-08-25 2021-11-23 湖南稀土金属材料研究院有限责任公司 La-Ti合金靶及其制备方法
CN115369258A (zh) * 2022-08-04 2022-11-22 江苏鑫瑞崚新材料科技有限公司 一种低银低硫超高纯铜提纯真空熔炼工艺

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5386603A (en) 1977-10-11 1978-07-31 Daido Steel Co Ltd Production of active metal ingot by plasma arc melting
JPH11246919A (ja) 1998-03-03 1999-09-14 Natl Res Inst For Metals 溶融金属の精製方法
JP2006122920A (ja) 2004-10-26 2006-05-18 Kobe Steel Ltd 活性高融点金属含有合金の長尺鋳塊製造法
JP2013049084A (ja) 2011-08-31 2013-03-14 Kobe Steel Ltd チタンまたはチタン合金からなるスラブの連続鋳造方法および連続鋳造装置
WO2016035824A1 (fr) 2014-09-04 2016-03-10 株式会社神戸製鋼所 PROCÉDÉ DE DÉSOXYDATION D'UN ALLIAGE Ti-Al
JP2017032273A (ja) 2015-07-31 2017-02-09 ダイキン工業株式会社 空気調和機
JP2017079928A (ja) 2015-10-26 2017-05-18 ホシザキ株式会社 冷温蔵装置
JP2017197905A (ja) 2016-04-25 2017-11-02 シバタ工業株式会社 砂防堰堤の補強構造体の施工方法及び砂防堰堤の補強構造体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5386603A (en) 1977-10-11 1978-07-31 Daido Steel Co Ltd Production of active metal ingot by plasma arc melting
JPH11246919A (ja) 1998-03-03 1999-09-14 Natl Res Inst For Metals 溶融金属の精製方法
JP2006122920A (ja) 2004-10-26 2006-05-18 Kobe Steel Ltd 活性高融点金属含有合金の長尺鋳塊製造法
JP2013049084A (ja) 2011-08-31 2013-03-14 Kobe Steel Ltd チタンまたはチタン合金からなるスラブの連続鋳造方法および連続鋳造装置
WO2016035824A1 (fr) 2014-09-04 2016-03-10 株式会社神戸製鋼所 PROCÉDÉ DE DÉSOXYDATION D'UN ALLIAGE Ti-Al
JP2017032273A (ja) 2015-07-31 2017-02-09 ダイキン工業株式会社 空気調和機
JP2017079928A (ja) 2015-10-26 2017-05-18 ホシザキ株式会社 冷温蔵装置
JP2017197905A (ja) 2016-04-25 2017-11-02 シバタ工業株式会社 砂防堰堤の補強構造体の施工方法及び砂防堰堤の補強構造体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3586998A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110629180A (zh) * 2019-10-16 2019-12-31 河北冠靶科技有限公司 一种应用于靶材的大尺寸无氧铜锭的生产装置及方法
CN113684456A (zh) * 2021-08-25 2021-11-23 湖南稀土金属材料研究院有限责任公司 La-Ti合金靶及其制备方法
CN115369258A (zh) * 2022-08-04 2022-11-22 江苏鑫瑞崚新材料科技有限公司 一种低银低硫超高纯铜提纯真空熔炼工艺

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