US20130071284A1 - Titanium alloy complex powder containing copper powder, chromium powder or iron powder, titanium alloy material consisting of this powder, and process for production thereof - Google Patents

Titanium alloy complex powder containing copper powder, chromium powder or iron powder, titanium alloy material consisting of this powder, and process for production thereof Download PDF

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US20130071284A1
US20130071284A1 US13/701,159 US201113701159A US2013071284A1 US 20130071284 A1 US20130071284 A1 US 20130071284A1 US 201113701159 A US201113701159 A US 201113701159A US 2013071284 A1 US2013071284 A1 US 2013071284A1
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powder
titanium alloy
chromium
iron
hip
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Osamu Kano
Hideo Takatori
Satoshi Sugawara
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Toho Titanium Co Ltd
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Assigned to TOHO TITANIUM CO., LTD. reassignment TOHO TITANIUM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KANO, OSAMU, SUGAWARA, SATOSHI, TAKATORI, HIDEO
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    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F8/00Manufacture of articles from scrap or waste metal particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09Mixtures of metallic powders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/023Hydrogen absorption
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • C22C1/0458Alloys based on titanium, zirconium or hafnium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies

Definitions

  • the present invention relates to titanium alloy complex powder containing copper powder, chromium powder or iron powder, titanium alloy material consisting of the powder and a process for production thereof, and in particular, relates to titanium alloy material having superior mechanical properties and relates to a process for production thereof.
  • Titanium alloy in particular, Ti-6Al-4V alloy has been well known as a material for airplanes.
  • the titanium alloy is produced by a vacuum arc remelting method or an electron beam remelting method.
  • the vacuum arc remelting method is a process in which Al—V master alloy is added to titanium material at an appropriate amount, this is pressed into briquettes, the briquettes are mutually bonded to form an electrode for remelting, the electrode for remelting is set in the vacuum arc remelting furnace, and the electrode is remelted in the vacuum to produce alloy ingots.
  • the electron beam remelting method is a process in which material for remelting consisting of titanium material and Al—V master alloy is supplied to a hearth, an electron beam is irradiated on the material to remelt it, and the melted metal is poured into a mold arranged downstream of the hearth to produce alloy ingots.
  • the alloy produced with powder material is greatly advantageous from the viewpoint of segregation compared to an alloy produced by the remelting method in which an ingot is solidified from the lower side to the upper side progressively.
  • the alloy is not produced via a step of being melted metal, there is no problem of evaporation of a low-melting point component. In this way, the powder method process for production of titanium alloy has several advantages compared to the remelting method.
  • the titanium alloy powder used in the powder method has inferior workability and formability, as a result, there is another problem that sintering density is difficult to increase.
  • Ti-6Al-4V alloy has small plastic deformability, it is known that sintering density is difficult increase by an ordinary method in the powder method (See Reference 1 below).
  • CIP Cold Isostatic Press
  • HIP Hot Isostatic Press
  • an upper limit of remaining pores in titanium alloy after sintering is controlled to be not more than 50 ⁇ m in the Reference 2.
  • a dense alloy having further fine pores or having no pores substantially is required as a material to which further higher strength is required compared to conventional titanium alloy.
  • An object of the present invention is to provide titanium alloy powder having superior quality by the powder method using titanium alloy scrap or titanium alloy ingot as a raw material, titanium alloy material, and a process for production thereof.
  • titanium alloy complex powder having uniform composition can be produced, by using the titanium alloy scrap or titanium alloy ingot as a raw material, hydrogenating it to generate hydrogenated titanium alloy, dehydrogenating it to generate titanium alloy powder, and further adding copper powder, chromium powder or iron powder, and thus the present invention has been completed.
  • titanium alloy complex powder having copper powder, chromium powder or iron powder can be consolidated to not less than 99% of theoretical density by CIP process and subsequent HIP process or by HIP process after filling the titanium alloy complex powder into a capsule, and thus, the present invention has been completed.
  • titanium alloy complex powder of the present invention has titanium alloy powder, and at least one kind of metallic powder selected from copper powder, chromium powder and iron powder added to the titanium alloy powder, wherein the added amount of the metallic powder is in a range from 1 to 10 wt % in the case in which one metallic powder is added, and the added amount of the metallic powder is in a range from 1 to 20 wt % in the case in which two or more metallic powders are added.
  • the titanium alloy powder contain aluminum and vanadium, or contain at least one kind selected from zirconium, tin, molybdenum, iron and chromium in addition to aluminum and vanadium.
  • the average particle size of the copper powder, chromium powder or iron powder be in a range from 1 to 300 ⁇ m.
  • a process for production of titanium alloy complex powder of the present invention has steps of hydrogenating titanium alloy raw material to generate hydrogenated titanium alloy powder, dehydrogenating the hydrogenated titanium alloy powder to generate titanium alloy powder, and adding at least one of copper powder, chromium powder or iron powder.
  • a process for production of titanium alloy material of the present invention has steps of consolidating the titanium alloy complex powder by CIP process and subsequent HIP process, or by HIP process after filling into a capsule.
  • a titanium alloy material of the present invention is produced by using titanium alloy powder as a raw material which is produced by the process having steps of hydrogenating titanium alloy raw material to generate hydrogenated titanium alloy powder, dehydrogenating the hydrogenated titanium alloy powder to generate titanium alloy powder, and adding at least one of copper powder, chromium powder or iron powder.
  • a true density of the titanium alloy material produced by the above process be not less than 99% of theoretical density.
  • titanium alloy material of the present invention is produced not via remelting and solidifying, segregation of copper, chromium or iron does not occur, and as a result, although it has been conventionally regarded as difficult to disperse or solid solve by the remelting method, copper, chromium or iron can be added at high concentration. Furthermore, since reactions between titanium alloy powder and copper powder, chromium powder or iron powder occur in consolidating processes, and no special technique such as mechanical alloying or the like is necessary in the mixing step.
  • FIG. 1 is a flow chart diagram showing the process for production of titanium alloy material of the present invention.
  • FIG. 2 is a SEM photograph of Ti-6Al-4V alloy powder produced by the hydrogenating and dehydrogenating processes.
  • FIG. 3 is a SEM photograph of titanium alloy complex powder in which copper powder is added to titanium alloy powder.
  • FIG. 4 is a result of EPMA analysis of 5% Cu containing Ti-6Al-4V alloy material in width direction.
  • FIG. 1 shows a desirable embodiment for production of titanium alloy material of the present invention.
  • a raw material of titanium alloy a mixture consisting of a master alloy powder having desired components produced in another process and pure titanium powder can be used; however, since the master alloy powder is expensive, it is desirable to use an alloy scrap or titanium alloy ingot originally having desired components such as titanium alloy chips, titanium alloy forged chips, edge material of titanium alloy rods or the like as the raw material in the present invention from the viewpoint of cost reduction.
  • titanium alloy raw material titanium alloy scraps or titanium alloy ingots
  • block shaped alloy scrap such as the forged chips
  • the alloy raw material is titanium alloy ingot, it is desirable to treat it so as to be cut chips.
  • the titanium alloy raw material treated and controlled as mentioned above is brought into the hydrogenating process under a hydrogen atmosphere.
  • the hydrogenating process is desirably performed in a temperature range from 500 to 650° C. Since hydrogenating process reaction of alloy raw material is an exothermic reaction, any heating operation by a heating furnace is not necessary accompanied by promotion of hydrogenating reaction, and thus hydrogenating reaction can be promoted automatically.
  • the titanium alloy raw material which is hydrogenation treated (hereinafter simply referred to as “hydrogenated titanium alloy”) is then cooled to room temperature, and it is desirably ground and sifted until hydrogenated titanium powder has a predetermined particle size under an inert atmosphere such as argon gas or the like.
  • hydrogenated titanium alloy powder that is ground and sifted is desirably heated until it reaches a high temperature range in an atmosphere held at reduced pressure.
  • the temperature of dehydrogenating process is desirably performed in a range from 500 to 800° C. Since the dehydrogenation reaction is an endothermic reaction, in contrast to the above-mentioned hydrogenation reaction, heating operation is necessary until hydrogen is completely generated from hydrogenated titanium alloy powder. By the operation, titanium alloy powder of the present invention can be obtained.
  • titanium alloy powder of the present invention be controlled in a range from 1 to 300 ⁇ m.
  • Titanium alloy powder obtained by the above-mentioned dehydrogenating process is sometimes sintered together, and in this case, it is desirable that the grinding and sifting processes be performed again.
  • the titanium alloy complex powder of the present invention After dehydrogenating process, by adding copper powder, chromium powder or iron powder which is a third component used in the present invention to the titanium alloy powder ground and sifted, the titanium alloy complex powder of the present invention can be obtained. It is desirable that the titanium alloy complex powder of which grinding and sifting processes be performed and copper powder, chromium powder or iron powder be added controlled in a range from 1 to 300 ⁇ m.
  • the consolidating process be performed by combining CIP and HIP appropriately.
  • titanium alloy complex powder obtained in the above-mentioned method be filled in a CIP rubber, treated at 100 to 200 MPa, then filled in a HIP capsule, and HIP treated at a temperature not more than ⁇ transformation point at 50 to 200 MPa for 1 to 5 hours. After such CIP process and subsequent HIP process, consolidated titanium alloy material can be obtained.
  • titanium alloy complex powder obtained in the above-mentioned method be filled in a HIP capsule and HIP treated at a temperature not higher than ⁇ transformation point at pressure from 50 to 200 MPa for 1 to 5 hours without CIP process.
  • Consolidated titanium alloy material can also be obtained by only the HIP process.
  • the ratio of adding be 1 to 10% of titanium alloy powder weight in the case in which one kind of these metallic powders is added.
  • the total ratio of adding be 1 to 20% of titanium alloy powder weight in the case in which two kinds or more of these metallic powders are added.
  • iron or chromium is originally contained in titanium alloy powder
  • addition ratio of copper powder, chromium powder or iron powder which is the third component and is alone added to titanium alloy powder is not more than 1%, effect of the consolidation cannot be exhibited sufficiently in the consolidating process in the sintering process.
  • addition ratio of copper powder, chromium powder or iron powder is more than 10%, strength of titanium alloy is undesirably deteriorated.
  • copper powder, chromium powder or iron powder used in the present invention has a purity of 2N5 to 4N5.
  • chromium powder or iron powder added to titanium alloy powder commercially available powder sample can be used.
  • powder sample powder that is obtained by grinding a block sample and then sifting can be used.
  • Titanium alloy powder to which copper powder, chromium powder or iron powder is added is consolidated by performing CIP process and subsequent HIP process, or by performing HIP process after filling titanium alloy powder into a capsule.
  • CIP process in the case of an alloy in which copper powder, chromium powder or iron powder is added to Ti-6Al-4V alloy, it is desirable to perform CIP process at 900° C. which is not higher than ⁇ transformation point and at hydrostatic pressure of 100 to 200 MPa and then to perform HIP process at a hydrostatic pressure of 100 MPa for 1 hour.
  • Titanium alloy material having a density not less than 99% can be obtained by such consolidating process.
  • Copper powder, chromium powder or iron powder added in titanium alloy powder is dispersed in titanium of alloy material matrix during a consolidating process, and as a result, alloy in which atoms of copper, chromium or iron are uniformly solid solved in titanium alloy can be produced.
  • titanium alloy copper, chromium or iron that is solid solved in titanium alloy can be solid solved at high ratio compared to a conventional remelting method, that is, 1 to 10 wt % in single powder addition and 1 to 20 wt % in plural powder addition. As a result, mechanical properties of titanium alloy material can be effectively controlled.
  • titanium alloy such as Ti-6Al-4V alloy, Ti-3Al-2.5V alloy, Ti-6Al-2Sn-4Zr-6Mo alloy, Ti-6Al-6V-2Sn alloy, Ti-10V-2Fe-3A1 alloy (10-2-3), Ti-5Al-4V-0.6Mo-0.4Fe alloy (Ti metal 54M), Ti-4.5Al-3V-2Fe-2Mo alloy (SP700), Ti-15V-3Cr-3Al-3Sn alloy (15-3-3-3), Ti-4Al-2.5V-1.5Fe alloy (ATI425), Ti-5Al-5V-5Mo-3Cr alloy (Ti-5553) can be used as the above mentioned raw material of titanium alloy powder.
  • Ti-6Al-4V alloy Ti-3Al-2.5V alloy
  • Ti-6Al-2Sn-4Zr-6Mo alloy Ti-6Al-6V-2Sn alloy
  • Ti-10V-2Fe-3A1 alloy 10-2-3
  • Ti-5Al-4V-0.6Mo-0.4Fe alloy Ti-4.5Al-3V-2Fe
  • Mechanical properties of titanium alloy material containing copper, chromium or iron and being consolidated by the above-mentioned method can be further controlled by subsequent processing such as rolling, extrusion or drawing and heat process.
  • Scrap cut chips of Ti-6Al-4V alloy were cut into chips having lengths not greater than 10 mm.
  • the chips were inserted into a container and the container was set in a furnace. After vacuum evacuation inside the furnace, heating was started, hydrogen was induced into the furnace after the temperature inside the furnace reached 300° C., and heating was continued until 650° C. while maintaining the inside of the furnace in a slightly pressurized condition by hydrogen. During this process, since Ti-6Al-4V alloy scrap chips and hydrogen are reacted and temperature inside the furnace is increased, heater output was set at 0, and the condition was maintained as it was until the reaction was completed.
  • FIG. 2 shows an SEM photograph of titanium alloy powder obtained as above. It was confirmed that alloy powder having relatively even particle size can be obtained by the method of the present invention in the photograph.
  • Electrolytic copper powder (particle size: not greater than 45 ⁇ m, produced by JX Nippon Mining & Metals Corporation) was added to titanium alloy powder of Example 1 at 5 wt % of titanium alloy powder, and they were mixed with a V-type mixing machine.
  • FIG. 3 shows an SEM photograph of titanium alloy complex powder obtained as above. It was confirmed that titanium alloy complex powder having relatively even particle size can be obtained by the method of the present invention in the photograph. Maximal particle size of obtained mixture powder was 300 ⁇ m, and average particle size was 60 ⁇ m.
  • Cu-added titanium alloy powder of Example 2 was filled in a CIP rubber, and CIP treated at 100 MPa. Density of the CIP compact was 65%. It has strength sufficient to be self-supported, and it was never broken during handling.
  • the CIP compact was encapsulated in a soft steel capsule and HIP treated. Conditions of HIP were 900° C., 100 MPa and 1 hr. After HIP process, titanium material was taken out and its density was measured, and it was not less than 99%. Density mentioned here means the ratio of apparent density against the theoretical density.
  • Cu-added titanium alloy powder of Example 2 was encapsulated in a soft steel capsule and HIP treated. Conditions of HIP were 900° C., 100 MPa and 1 hr. After HIP process, titanium alloy material was taken out and its density was measured, and it was not less than 99%. Density mentioned here means the ratio of apparent density against the theoretical density.
  • Titanium alloy material of Example 3 was analyzed by EPMA along a range of 10.5 mm to confirm variation of each component of Ti, Al, V and Cu, and the results are shown in FIG. 4 . It is confirmed that concentration of Cu is almost uniform around 5% along the analyzed range of 10.5 mm.
  • Chromium powder was added to titanium alloy powder of Example 1 at 5 wt % of titanium alloy powder to obtain Cr containing titanium alloy powder.
  • Cr powder was prepared by crushing electrolytic chromium powder produced by Japan Metals & Chemicals Co., Ltd., and sifting it by using a sifter of 50 mesh.
  • Cr containing titanium alloy material was obtained by CIP process and subsequent HIP process in a similar conditions of Example 3. Density of the material was not less than 99%.
  • Chromium added titanium alloy powder of Example 5 was encapsulated in a soft steel capsule and HIP process was performed.
  • HIP condition was 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Iron powder was added to titanium alloy powder of Example 1 at 5 wt % of titanium alloy powder to obtain Fe containing titanium alloy powder.
  • Fe powder was commercially available atomized iron powder, and its average particle diameter was 4 ⁇ m.
  • Fe containing titanium alloy material was obtained by CIP process and subsequent HIP process in a similar conditions of Example 3. Density of the material was not less than 99%.
  • Iron added titanium alloy powder of Example 6 was encapsulated in a soft steel capsule and HIP process was performed. HIP conditions were 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Cu powder and Fe powder were added to titanium alloy powder of Example 1 at 5 wt % (each powder), 10 wt % (total powders of Cu+Fe) of titanium alloy powder to obtain Cu—Fe containing titanium alloy powder.
  • Cu powder and Fe powder were the same powders as in Examples 2 and 6 respectively.
  • Cu—Fe containing titanium alloy material was obtained by CIP process and subsequent HIP process in the similar conditions of Example 3. Density of the material was not less than 99%.
  • HIP process Cu powder and Fe powder added titanium alloy powder of Example 7 was encapsulated in a soft steel capsule and HIP process was performed. HIP conditions were 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Cu powder and Cr powder were added to titanium alloy powder of Example 1 at 5 wt % (each powder), 10 wt % (total powders of Cu+Cr) of titanium alloy powder to obtain Cu—Cr containing titanium alloy powder.
  • Cu powder and Cr powder were the same powders as in Examples 2 and 5 respectively.
  • Cu—Cr containing titanium alloy material was obtained by CIP process and subsequent HIP process in the similar conditions of Example 3. Density of the material was not less than 99%.
  • HIP condition was 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Cr powder and Fe powder were added to titanium alloy powder of Example 1 at 5 wt % (each powder), 10 wt % (total powders of Cr+Fe) of titanium alloy powder to obtain Cr—Fe containing titanium alloy powder.
  • Cr powder and Fe powder were the same powders as in Examples 5 and 6 respectively.
  • Cr—Fe containing titanium alloy material was obtained by CIP process and subsequent HIP process in the similar conditions of Example 3. Density of the material was not less than 99%.
  • HIP process Cr powder and Fe powder added titanium alloy powder of Example 9 was encapsulated in a soft steel capsule and HIP process was performed. HIP conditions were 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Cu powder, Cr powder and Fe powder were added to titanium alloy powder of Example 1 at 4 wt % (each powder), 12 wt % (total powders of Cu+Cr+Fe) of titanium alloy powder to obtain Cu—Cr—Fe containing titanium alloy powder.
  • Cu powder, Cr powder and Fe powder were the same powders as in Examples 2, 5 and 6 respectively.
  • Cu—Cr—Fe containing titanium alloy material was obtained by CIP process and subsequent HIP process in the similar conditions of Example 3. Density of the material was not less than 99%.
  • HIP process was performed. HIP conditions was 900° C., 100 MPa, and 1 hour. After HIP process, titanium alloy material was taken out and the density was measured, and the density was not less than 99%.
  • Cu powder was each added at 1%, 3%, 8% and 10% in a way completely similar to that of Example 2 to obtain four samples of Cu containing titanium alloy powder.
  • Cu containing titanium alloy material was obtained by CIP process and subsequent HIP process in similar conditions of Example 3. Densities of all the materials were not less than 99%. Vickers hardnesses thereof were measured, and the results are shown in Table 1. In Table 1, the result of 5 wt % containing alloy of Example 4 is also shown.
  • Titanium alloy powder the as same as in Example 1 was CIP treated in a manner similar to that of Example 3 without adding Cu, Cr and Fe powder.
  • a CIP compact does not have sufficient strength, and a corner part was broken right after removal. Although the part was broken, an attempt was made to handle the CIP compact so as to be encapsulated into a HIP container. Then, the compact broke at a central part into two pieces, and HIP process could not be performed.
  • CIP process was performed similarly at 200 MPa of hydrostatic pressure, and the compact could be completed. The compact was carefully handled to be encapsulated in a HIP container, and HIP was performed in conditions similar to that of Example 3. The compact was taken out of the HIP container and density was measured, and the density was 98%.
  • the present invention provides titanium alloy complex powder, consolidated titanium alloy material and process for production thereof, using titanium alloy scrap or ingot as a raw material and by a hydrogenation and dehydrogenation method.

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