WO2012147998A1 - α+β型またはβ型チタン合金およびその製造方法 - Google Patents
α+β型またはβ型チタン合金およびその製造方法 Download PDFInfo
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- WO2012147998A1 WO2012147998A1 PCT/JP2012/061782 JP2012061782W WO2012147998A1 WO 2012147998 A1 WO2012147998 A1 WO 2012147998A1 JP 2012061782 W JP2012061782 W JP 2012061782W WO 2012147998 A1 WO2012147998 A1 WO 2012147998A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/023—Hydrogen absorption
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
Definitions
- the present invention relates to a titanium alloy, and in particular, a titanium alloy having a composition which is superior to mechanical properties such as strength and hardness compared to Ti-6Al-4V alloy and the like and can not be manufactured by the conventional melting method. , The manufacturing method of the titanium alloy which can manufacture the alloy in low cost.
- titanium alloys are expanding not only for aircraft but also for the consumer market, and demand for such alloys is increasing year by year.
- alloys for aircraft have high quality and function requirements, so high quality is the top priority, and manufacturing cost reduction is often the next issue.
- Ti-6Al-4V alloy (hereinafter sometimes referred to as 64 alloy) has been used for a long time because it has excellent mechanical properties.
- 64 alloy has poor machinability, there is a problem that it is difficult to apply to complicated parts of the shape.
- Ti-4.5Al-3V-2Fe-2Mo alloy (so-called SP700) was developed to improve the processability of the 64 alloy.
- Ti-10V-2Fe-3Al a so-called 10-2-3 alloy
- Ti-15V-3Cr-3Al-3Sn a so-called 15-3-3-3
- vanadium, iron and the like are easily segregated in any of the SP700, 10-2-3, and 15-3-3-3-3 alloys, and further improvement is required.
- Non-Patent Document 1 it has been reported that by adding 1% copper to pure titanium, the processability of the titanium material is further improved (see, for example, Non-Patent Document 1).
- copper has a large segregation in titanium and is difficult to add in excess of 1% with respect to titanium, which further restricts the improvement of the characteristics of the alloy, and an improvement is required.
- the elemental powder mixing method is a method in which powders of constituent elements constituting the target alloy are separately prepared, and composite powder obtained by uniformly mixing these powders is used as a starting material of a titanium alloy.
- the cost of the titanium powder is due to the high price of the pure titanium material used, and further improvement is required.
- the object of the present invention is, as described above, to provide a copper-containing titanium alloy having a composition which can not be realized by the conventional method in which copper is contained without segregation in titanium, and whose strength and hardness are improved. It is.
- another object of the present invention is to provide a method for producing the copper-containing titanium alloy inexpensively as compared to the conventional method.
- the titanium alloy produced by the above-described method exhibits not only high strength but also excellent hardness, as compared to titanium alloys produced by the conventional method, because the concentration segregation of the alloy components is small. It plays.
- the ⁇ + ⁇ -type or ⁇ -type titanium alloy according to the present invention contains 1 to 10 mass% of copper, and the crystal phase is either ⁇ phase or ⁇ phase and ⁇ phase, and the crystal phase is 100 ⁇ m or less It is characterized in that it is composed of crystal grains, and the copper concentration per 1 mm 3 of any part of the crystal phase is within ⁇ 40% as compared with any other part.
- the ⁇ + ⁇ -type or ⁇ -type titanium alloy according to the present invention is obtained by pressing and forming a mixed powder of copper powder and titanium alloy powder under heating. is there.
- the titanium alloy powder is manufactured using a titanium alloy as a raw material, and the titanium alloy includes aluminum, vanadium, molybdenum, iron, chromium, It is a preferable embodiment that at least one or more elements are contained in tin.
- the method for producing ⁇ + ⁇ -type titanium alloy or ⁇ -type titanium alloy according to the present invention is a method for producing copper-containing ⁇ + ⁇ -type titanium alloy or ⁇ -type titanium alloy, wherein 1 to 10 mass% of copper powder and titanium alloy powder It is characterized in that pressure molding is carried out under heating to obtain a compact.
- the pressure forming temperature (Tw (° C.)) under the above heating is (Td ⁇ 100 ° C.) ⁇ Tw ⁇ (Td + 100 ° C.) (In this case, Td (° C.) represents the ⁇ transformation point of the pressure-formed titanium alloy).
- the titanium alloy powder is produced using a titanium alloy as a raw material, and aluminum, vanadium, It is a preferable embodiment that at least one or more metal elements are contained among molybdenum, iron, chromium and tin.
- the composition contains a high concentration of copper which can not be produced by the conventional method, and has no composition of copper segregation.
- the titanium alloy of the hard and hard material can be manufactured at low cost.
- the titanium alloy according to the present invention has an effect that it can be suitably used in the fields of high strength machine parts, medical materials, and aircraft materials.
- the ⁇ + ⁇ type or ⁇ type titanium alloy according to the present invention contains 1 to 10 mass% of copper, and the crystal phase is either ⁇ phase or ⁇ phase and ⁇ phase, and is composed of crystal grains of 100 ⁇ m or less, In addition, it is characterized in that the copper concentration per 1 mm 3 of any part of the crystal phase is within ⁇ 40% as compared with any other part.
- the titanium alloy according to the present invention has an alloy structure due to the feature that the copper concentration per 1 mm 3 of any part of the above-mentioned crystal phase is suppressed within ⁇ 40% as compared with any other part. The whole is kept sufficiently uniform.
- the ⁇ + ⁇ -type or ⁇ -type titanium alloy according to the present invention is characterized in that it is manufactured by pressure forming under heating of a titanium alloy powder containing 1 to 10 mass% of copper powder.
- a titanium alloy powder containing 1 to 10 mass% copper powder means a composite powder obtained by adding and mixing a separately prepared copper powder to a titanium alloy powder not containing a copper powder.
- titanium alloy powder containing aluminum or vanadium As a preferable example of such an alloy powder, Ti-6Al-4V alloy powder, Ti-3Al-2.5V alloy powder, etc. are mentioned.
- alloy powder containing molybdenum or iron, or chromium or tin as appropriate may be used. These representative alloy powders are listed below. Ti-10V-2Fe-3Al alloy powder, Ti-15V-3Al-3Al-3Cr-3Sn alloy powder, Ti-4.5Al-3V-2Fe-2Mo alloy powder, Ti-5Al-5V-5Mo-3Cr alloy powder, Ti-5Al-4V-0.6Mo-0.4Fe alloy powder
- the above-mentioned titanium alloy powder uses as a raw material cutting chips and scraps of ingots, and is preferably manufactured by a hydrodehydrogenation method (hereinafter sometimes referred to as "HDH method"). It is.
- FIG. 1 shows a preferred embodiment of the process involved in the production of a titanium alloy according to the present invention.
- a titanium alloy raw material to be provided in the present invention an alloy scrap or titanium alloy ingot having a desired component from the beginning such as titanium alloy chips, titanium alloy forgings, or scraps of titanium alloy rods can be used. .
- titanium alloy raw materials may preferably be dimensioned to a predetermined length or size in advance.
- alloy chips it is preferable to cut in advance to a length of 100 mm or less. By cutting into the length as described above, it is possible to efficiently advance the hydrogenation step of the next step.
- block-shaped alloy scrap such as forged pieces, there is no particular need for pre-treatment, as long as it is large enough to enter the hydrogenation furnace.
- the alloy material is a titanium alloy ingot, it is preferable to use chips.
- the titanium alloy raw material prepared as described above is subjected to a hydrotreating step under a hydrogen atmosphere.
- the hydrogenation treatment is preferably performed in a temperature range of 500 to 650 ° C. Since the hydrotreating reaction of the alloy raw material is an exothermic reaction, the temperature raising operation by the heating furnace is unnecessary with the progress of the hydrogenation reaction, and there is an effect that the hydrogenation reaction can be spontaneously proceeded. is there.
- the hydrotreated titanium alloy raw material (hereinafter sometimes simply referred to as “hydrogenated titanium alloy”) may be crushed and sieved to a predetermined particle size in an inert atmosphere such as argon gas after cooling to room temperature. It is preferable to separate.
- the dehydrogenation temperature is preferably performed while evacuation in a temperature range of 500 ° C. to 800 ° C. Since the dehydrogenation reaction is an endothermic reaction unlike the above-mentioned hydrotreating reaction, a heating operation is required until generation of hydrogen from the titanium hydride alloy powder disappears.
- the titanium alloy powder according to the present invention can be obtained by the above operation.
- the titanium alloy powder according to the present invention is preferably sized in the range of 1 to 300 ⁇ m, and more preferably 5 to 150 ⁇ m. If the particle size is larger than this range, the density of the alloy of the final product tends to be difficult to increase, while if it is smaller than this range, the bulk density decreases and it is easily oxidized to increase the oxygen content, burn, etc. An inconvenience arises.
- the titanium alloy powder obtained by the completion of the dehydrogenation treatment may be mutually sintered. In this case, it is preferable to appropriately perform the crushing treatment.
- the present invention is characterized in that 1 to 10 mass% of copper powder is blended to the titanium alloy powder produced by the above method.
- the strength and hardness of the titanium alloy material obtained by pressure forming the above-mentioned alloy powder as a raw material are maintained at a high level. It has the effect of being able to
- the particle size of the copper powder to be added to the titanium alloy powder is preferably adjusted to 1 to 300 ⁇ m. More preferably, use of a copper powder in the range of 1 to 50 ⁇ m is a preferred embodiment.
- the use of finer copper powder is advantageous for producing uniform titanium alloy powder, so the average particle size (d50) of copper powder is 10 to 40 ⁇ m in the range of 1 to 50 ⁇ m described above. It is preferable to adjust to be in the range of
- extrusion under heating can be applied to pressure molding used in the present invention, in particular, in the case of using extrusion under heating, The effect of simultaneously advancing sintering and shape forming in a short time is also exhibited, and an excellent effect is obtained in terms of productivity.
- the titanium alloy powder mixed with the copper powder is subjected to pressure forming under heating after being filled in a metal capsule.
- the titanium alloy material obtained by extruding a titanium alloy powder obtained by compounding copper powder filled in a metallic capsule is a titanium alloy containing copper of a high composition which could not be manufactured by the conventional method, and the segregation of copper is It exhibits excellent mechanical properties such as low strength, high strength and high hardness.
- Tw the temperature of the above-mentioned pressure molding into the range of (Td-100 ° C) ⁇ Tw ⁇ (Td + 100 ° C).
- Td means the ⁇ transformation point of the titanium alloy to be subjected to pressure forming.
- the pressure forming temperature is lower than (Td-100 ° C.)
- the deformation resistance of the titanium alloy powder is large, and it is difficult to fully densify the titanium alloy powder even after the pressure forming. is there.
- the material may be clogged in the die, which is not preferable.
- the compacting temperature is higher than (Td + 100 ° C.)
- the crystal grains of the titanium alloy material tend to be coarsened to 100 ⁇ m or more, and the titanium alloy It is not preferable because it adversely affects the mechanical properties of the material.
- the crystal structure of the pressure-formed titanium alloy material according to the present invention is Because they are uniform and miniaturized, they are not only strong and hard, but also exhibit excellent mechanical properties with a good balance between tensile strength and elongation.
- the titanium alloy according to the present invention contains copper having a composition of 1 to 10 mass%, and the value of the concentration of copper per 1 mm 3 in any part of the alloy is the concentration of copper in any other part. It is characterized in that it is within ⁇ 40% of the value.
- the above aspect means that copper in the titanium alloy according to the present invention is uniformly distributed.
- the tensile strength is as high as 1400 to 1550 MPa and the elongation is as high as 2 to 7%, and the tensile strength is superior to conventional alloys. Not only strength but also excellent elongation can be obtained.
- the titanium alloy having such excellent mechanical properties is manufactured by densifying it using, as a raw material, an alloy powder obtained by pulverizing an alloy obtained by a melting method called a pre-alloy method, among others. Is a preferred embodiment.
- the "pre-alloying method” means using the powder manufactured using the alloy manufactured by the melting method as a raw material as a sintering raw material, and separately preparing metal powders composed of individual components It corresponds to the raw powder mixed powder obtained by uniformly mixing these metal powders.
- titanium alloy powder and copper powder of the target composition are prepared and mixed uniformly, and then the mixed powder is charged into a metal capsule, and then the inside of the capsule is put into a vacuum of 10 -1 Torr or less. After molding, it is preferable to press-mold by HIP, CIP-baking or extrusion. It is also preferred that the powder be filled in a die and hot pressed at a vacuum of 10 -2 Torr or less.
- the pressure molding temperature (Tw) under heating is preferably in the range of (Td ⁇ 100 ° C.) ⁇ Tw ⁇ (Td + 100 ° C.).
- pressure forming under heating in the present invention can be achieved by using a known method such as HIP, hot press, CIP-HIP, or extrusion under heating.
- the ratio of the cross sectional area of the extruded titanium alloy material to the cross sectional area of the capsule inserted in the extrusion apparatus (
- the term “extrusion ratio” may be simply referred to as “1/10 to 1/30”.
- the degree of flow of the capsule in which the titanium alloy powder is embedded can be controlled, the degree of wrought of the extruded titanium alloy material can be adjusted, and more preferable mechanical properties are imparted.
- covers the titanium alloy material manufactured by methods, such as HIP in this invention, CIP-HIP, heating under heating, is isolate
- the titanium alloy material from which the capsule is separated in this manner may be again heated to a high temperature under a vacuum atmosphere.
- the strength of the titanium alloy material that has been subjected to the above-mentioned treatment is remarkably excellent, and it is suitably used for a structural material such as a high strength mechanical component because it has fine grains and is reinforced by uniformly distributed Cu.
- a structural material such as a high strength mechanical component because it has fine grains and is reinforced by uniformly distributed Cu.
- the strength of the titanium alloy material containing copper according to the present invention not only shows a value as high as 10 to 30% as compared with the conventional titanium alloy material not containing copper, but titanium alloy scrap is used as its raw material In this case, the cost of the raw material can be reduced, and as a result, the cost of the titanium alloy material which is the final product can be reduced by 50 to 70% as compared with the prior art.
- the titanium alloy material according to the present invention exhibits an effect of exhibiting a value as high as 10 to 30% in hardness as compared with a material to which copper is not added.
- the titanium alloy according to the present invention has excellent mechanical properties as described above, and as a result, it can be suitably applied not only to industrial precision machine parts but also to medical materials, and further, strength It has an effect that it can be suitably used not only for aircraft parts where abrasion resistance is also required.
- the said titanium alloy containing copper can be manufactured also by the melt
- the titanium alloy material produced in the present invention preferably contains at least aluminum and vanadium, but it may optionally contain molybdenum, iron, chromium, or tin. . These representative alloys are listed below. However, the alloys that can be produced in the present invention are not limited to these, and can be applied to various titanium alloys.
- Raw material 64 alloy powder Production method: After producing 64 alloy scraps by the HDH method, grinding and sizing average particle diameter (d50): 52 ⁇ m 2) Copper powder Production method: Electrolytic copper powder, manufactured by JX Nippon Mining & Metals Co., Ltd., trade name 51-N Average particle size (d50): 35 ⁇ m 3) Copper powder blending ratio to titanium alloy powder 1% to 10 mass% 4) Mixing The 64 alloy powder and the copper powder were homogenized using a commercially available mixer.
- the ⁇ transformation point (Td) of 64 alloy (0% copper) reported in the literature is set at 995 ° C., which is almost identical to that value.
- deformation resistance was determined at a temperature 30 ° C. lower than the ⁇ transformation point (Td) and the ⁇ transformation point (Td) determined above, and at a temperature 50 ° C. higher than the ⁇ transformation point (Td).
- the measurement was performed by a compression test using a hot working reproduction apparatus (Thermec Master Z, manufactured by Fuji Electric Radio Co., Ltd.). The results are shown below.
- the extrusion temperature was determined in consideration of the pushing power of the extrusion device and the deformation resistance of the material.
- a composite powder prepared by mixing 0%, 3%, 5%, 7% and 10% of copper powder in 64 alloy powder was filled in a mild steel capsule, and the inside was evacuated to 1 ⁇ 10 ⁇ 2 Torr and then enclosed.
- the powder-encapsulated capsule was formed by hot extrusion as an example of pressure forming under heating.
- the heating temperature of each copper content at this time was the temperature described in Table 3.
- the heating time was 2 hours.
- the heating temperature of each copper content alloy and the temperature difference from the ⁇ transformation point (Td) of the temperature are as shown in the table below.
- Example 1 Comparative Example 1
- the mechanical properties of the alloy powder with and without copper powder were investigated. As shown in Table 4, it was confirmed that the addition of the copper powder is superior in yield strength, tensile strength and hardness.
- the copper-added alloy results in a little reduction in elongation particularly when the material has a copper content of 5% or more, which was considered to be due to the fact that the pressure forming temperature is in the ⁇ temperature range.
- Example 2 (difference in pressure molding temperature) The effect of pressure forming temperature on the crystal structure of the sintered body obtained by pressure forming was examined for a Cu 5% -added 64 alloy (beta transformation point: 950 ° C.).
- a mixed phase structure of ⁇ phase and ⁇ phase was observed as shown in FIG.
- Comparative Example 2-1 in which the pressure molding temperature was out of the range of the present invention, the ⁇ phase in the crystal structure was coarsened. Further, in Comparative Example 2, the material was clogged in the die, and a pressure-formed material could not be obtained.
- Example 3 (Copper concentration distribution of manufactured titanium material)
- Example 2 the component concentration in the crystal structure of the titanium material produced by pressure molding was examined by EPMA.
- the respective X-ray images were obtained for Ti, Al, V and Cu. The image is shown in FIG. 3 and the results are shown below.
- the numbers shown here are EPMA count numbers, and the sensitivity differs depending on each element. Therefore, in order to convert the count number to a concentration, the average count number is shown as a nominal concentration of each element as shown in Table 6.
- the density correction factor was determined. Based on this correction factor, the existence ratio by concentration was determined as shown in Tables 7 and 8. The lowest and highest concentrations of each element were as follows.
- Example 1 and Example 1 were used except that mixed powder obtained by weighing and uniformly mixing aluminum powder (60 wt%) and vanadium powder (40%) in a predetermined amount instead of 64 alloy powder was used. Under the same conditions, a copper-added 64 alloy was produced.
- Comparative Example 4 (Alloy by Melting Method) In place of the alloy powder used in Example 1, 64 alloy ingots and electrolytic copper are prepared, and 3, 5, 10 wt% of electrolytic copper is compounded, and then a copper alloy 64 alloy ingot with ⁇ 100 is prepared using an electron beam melting furnace. I got
- Test pieces were cut out of the copper-containing 64 alloy ingot, the mechanical properties were investigated, and the results are summarized in Table 8.
- the tensile strength of the ingot melted in the comparative example showed a value 20% to 25% lower than that of Example 1.
- the distribution of copper in the ingot was examined with a CX-ray microanalyzer, and it was found that the Cu concentration was 0.3 to 0.5% and an average concentration over a wide area of 1 mm 3 or more. On the other hand, a region which is 1/10 or more diluted and a portion where Cu concentration is 20% to 40% and 10 times or more of the average concentration are observed.
- the titanium alloy according to the present invention has superior mechanical properties as compared to titanium alloys manufactured by the conventional melting method. Furthermore, by using the alloy powder produced by the pre-alloying method used in the present invention, the manufacturing cost can be reduced by 30 to 40%, despite showing mechanical properties equivalent to the elemental powder mixing method. It was confirmed that it could be manufactured.
- Example 4 (5% Cu added to Ti-10V-2Fe-3Al alloy powder)
- 5% of the electrolytic copper powder used in Example 1 was added to obtain a mixed powder composed of a Ti-10V-2Fe-3Al alloy powder and an electrolytic copper powder.
- the mixed powder was enclosed in a mild steel capsule and hot-extruded. Extrusion was carried out after heating to 800 ° C. for 2 hours.
- the observation of the structure of the extruded material, the tensile test, the measurement of hardness, and the EPMA observation were performed.
- the grain size, the yield strength, the tensile strength, the elongation and the hardness are shown in Table 9.
- Comparative Example 5 (Ti-10V-2Fe-3Al alloy powder, no copper powder added)
- the Ti-10V-2Fe-3Al alloy powder produced in Example 4 was sealed in a mild steel capsule without adding copper powder, and was hot-extruded.
- the extrusion conditions were the same as in Example 4.
- the structure observation of the extruded material, a tensile test, and hardness measurement were performed. The results are shown in Table 9.
- Example 5 (5% of copper powder is added to Ti-15V-3Al-3Cr-3Sn alloy powder)
- 5% of the electrolytic copper powder used in Example 1 was added to obtain a mixed powder consisting of a Ti-15V-3Al-3Cr-3Sn alloy powder and an electrolytic copper powder.
- the mixed powder was enclosed in a mild steel capsule and hot-extruded. Extrusion was carried out after heating to 750 ° C. for 2 hours.
- the observation of the structure of the extruded material, the tensile test, the measurement of hardness, and the EPMA observation were performed.
- the grain size, the yield strength, the tensile strength, the elongation and the hardness are shown in Table 9.
- Comparative Example 6 Ti-15V-3Al-3Cr-3Sn alloy powder, no copper powder added
- the Ti-15V-3Al-3Cr-3Sn alloy powder produced in Example 5 was sealed in a mild steel capsule without adding Cu powder, and was hot-extruded.
- the extrusion conditions were the same as in Example 5.
- the structure observation of the extruded material, a tensile test, and hardness measurement were performed. The results are shown in Table 9.
- Example 6 (5% copper powder added to Ti-4.5Al-3V-2Fe-2Mo alloy powder)
- 5% of the electrolytic copper powder used in Example 1 was added to obtain a mixed powder consisting of a Ti-4.5Al-3V-2Fe-2Mo alloy powder and an electrolytic copper powder.
- the mixed powder was enclosed in a mild steel capsule and hot-extruded. Extrusion was carried out after heating to 880 ° C. for 2 hours.
- the observation of the structure of the extruded material, the tensile test, the measurement of hardness, and the EPMA observation were performed.
- the grain size, the yield strength, the tensile strength, the elongation and the hardness are shown in Table 9.
- Comparative Example 7 (Ti-4.5Al-3V-2Fe-2Mo alloy powder, no copper powder added)
- the Ti-4.5Al-3V-2Fe-2Mo alloy powder produced in Example 6 was sealed in a mild steel capsule without addition of a copper powder, and was hot-extruded.
- the extrusion conditions were the same as in Example 6.
- the structure observation of the extruded material, a tensile test, and hardness measurement were performed. The results are shown in Table 9.
- Example 7 (5% copper powder is added to Ti-5Al-5V-5Mo-3Cr alloy powder)
- 5% of the electrolytic copper powder used in Example 1 was added to obtain a mixed powder consisting of Ti-5Al-5V-5Mo-3Cr alloy powder and copper powder.
- the mixed powder was enclosed in a mild steel capsule and hot-extruded. Extrusion was carried out after heating to 840 ° C. for 2 hours.
- the observation of the structure of the extruded material, the tensile test, the measurement of hardness, and the EPMA observation were performed.
- the grain size, the yield strength, the tensile strength, the elongation and the hardness are shown in Table 9.
- Example 8 (5% copper powder added to Ti-5Al-4V-0.6Mo-0.4Cr alloy powder)
- 5% of the electrolytic copper powder used in Example 1 was added to obtain a mixed powder composed of Ti-5Al-4V-0.6Mo-0.4Cr alloy powder and copper powder.
- the mixed powder was enclosed in a soft copper capsule and hot-extruded. Extrusion was carried out after heating to 900 ° C. for 2 hours.
- the observation of the structure of the extruded material, the tensile test, the measurement of hardness, and the EPMA observation were performed.
- the grain size, the yield strength, the tensile strength, the elongation and the hardness are shown in Table 9.
- the present invention relates to a titanium alloy by a powder method and a method for producing the same, which is a copper-containing titanium alloy having a composition which has been difficult to manufacture by the conventional method, which has no copper segregation, and further has strength and hardness. Not only that, but also in terms of cost, it can be manufactured at lower cost than before.
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Abstract
Description
本発明に係るα+β型またはβ型チタン合金は、1~10mass%の銅を含有し、その結晶相がβ相もしくはα相およびβ相のいずれかであり、100μm以下の結晶粒で構成され、しかも、かつ、該結晶相の任意の部位の1mm3当たりの銅濃度が、他の任意の部位に比べて±40%以内にあることを特徴とするものである。
Ti−10V−2Fe−3Al合金粉、
Ti−15V−3Al−3Al−3Cr−3Sn合金粉、
Ti−4.5Al−3V−2Fe−2Mo合金粉、
Ti−5Al−5V−5Mo−3Cr合金粉、
Ti−5Al−4V−0.6Mo−0.4Fe合金粉
特に、押出加工により加圧成形する場合にはダイス内に材料が詰まってしまう場合があるので好ましくない。
Ti−(13.5~15)V−(2.7~3)Cr−(2.7~3)Al−(2.7~3)Sn−(1~10)Cu、
Ti−(4.1~4.5)Al−(2.7~3)V−(1.8~2)Fe−(1.8~2)Mo−(1~10)Cu、
Ti−(4.5~5)Al−(4.5~5)V−(4.5~5)Mo−(2.7~3)Cr−(1~10)Cu、
Ti−(4.5~5)Al−(3.6−4)V−(0.5~0.6)Mo−(0.3~0.4)Fe−(1−10)Cu。
1.原料
1)64合金粉
製法:64合金スクラップをHDH法で製造した後、粉砕整粒
平均粒径(d50):52μm
2)銅粉
製法:電解銅粉、JX日鉱日石金株式会社製、商品名51−N
平均粒径(d50):35μm
3)チタン合金粉に対する銅粉配合比
1%~10mass%
4)混合
前記64合金粉および銅粉は、市販の混合機を用いて均一化した。
加温下での加圧成形条件を決定するために、64合金粉末に銅粉末を0%、3%、5%、7%、10%添加してサンプルを作り、β変態点(Td)とβ変態点(Td)近傍の温度における変形抵抗を求めた。β変態点(Td)は、試験片をアルゴンガス雰囲気中で昇温加熱しながら四端子法で電気抵抗を測定し、電気抵抗変化の温度依存性が変化する温度を変態点とした。装置は電気抵抗測定装置(商品名ARC−TER−1型)を用いた。この結果は以下の通りであった。
押出温度は、押出装置の押出力と、材料の変形抵抗を考慮して決定した。64合金粉末に銅粉末を0%、3%、5%、7%、10%混合した複合粉を軟鋼カプセルに充填し、内部を1×10−2Torrまで真空排気後封入した。この粉末封入カプセルを加温下の加圧成形の一例として熱間押出にて成形した。この時の各銅含有量の加熱温度は表3に記載の温度とした。加熱時間は2Hrとした。それぞれの銅含有量合金の加熱温度と、その温度のβ変態点(Td)からの温度差は下表の通りである。
加温下の加圧成形により生成したチタン合金材の表面に残留しているカプセルを酸洗により溶解除去した。
1)引張強度測定
インストロン社製の引張り試験機(型番:5985型)を使用した。
2)結晶組織観察
日本電子製の測定器EPMA(型番:JXA−8100)を使用した。
3)結晶組織中の銅の分布
日本電子製の測定器EPMA(型番:JXA−8100)を使用した。
64合金粉に、銅粉を添加した場合と、添加しない場合における機械的特性を調査した。表4に示すように、銅粉を添加した方が、降伏強さ、引張り強さ、硬さに優れていることが確認された。銅添加合金は特に銅含有量5%以上の材料で伸びがやや少ない結果となったが、これは、加圧成形温度がβ温度域であることが影響している、と考えられた。
Cu5%添加64合金(ベータ変態点:950℃)について、加圧成形して得られた焼結体の結晶組織に及ぼす加圧成形温度の影響を調べた。
加圧成形温度が本発明の範囲にある実施例2−1、実施例2−2においては、図2に示すようにβ相とα相の混相組織が観察された。これに対して加圧成形温度が本発明の範囲外にある比較例2−1においては、結晶組織中のβ相が粗大化していた。また、比較例2においては、ダイスの中で材料が詰まり、加圧成形材を得ることができなかった。
実施例2において、加圧成形により製造されたチタン材の結晶組織中の成分濃度をEPMAにて調べた。Ti、Al、V、CuについてそれぞれのX線像を求めた。画像を図3に示すとともに、その結果を以下に示す。ここで示している数字はEPMAのカウント数であり、それぞれの元素によって感度が違うので、カウント数を濃度に換算するために、平均カウント数を各元素の公称濃度として、表6に示すように濃度補正係数を求めた。この補正係数をもとに、濃度別の存在割合を表7および表8のように求めた。それぞれの元素の最低濃度と最高濃度は以下の通りであった。
Al(平均濃度5.7%)は、最低濃度3.8%~最高濃度8.6%
V(平均濃度3.8%)は、最低濃度3.0%~最高濃度4.8%
Cu(平均濃度5.0%)は、最低濃度2.0%~最高濃度8.2%
実施例1において、64合金粉の代わりに、アルミニウム粉(60wt%)とバナジウム粉(40%)を所定量秤量して均一混合して得られた混合粉を用いた以外は、実施例1と同じ条件下で、銅添加した64合金を製造した。
実施例1において用いた合金粉に代えて、64合金塊、および電解銅を準備して電解銅を3、5、10wt%配合した後、電子ビーム溶解炉を用いてφ100の銅入り64合金インゴットを得た。
Ti−10V−2Fe−3Al合金インゴットの切削切粉を水素化し、Ti−10V−2Fe−3Al合金の水素化物を製造、粉砕・篩別してD50=50μmの合金粉末を得た。この粉末に、実施例1で用いた電解銅粉を5%添加して、Ti−10V−2Fe−3Al合金粉と電解銅粉からなる混合粉末を得た。この混合粉末を軟鋼製カプセルに封入し、熱間押出加工した。押出は 800℃に2時間加熱した後に実施した。押出材の組織観察、引張り試験、硬さ測定、EPMA観察を行った。結晶粒径、降伏強さ、引張り強さ、伸び、硬さを表9に示す。
実施例4で製造したTi−10V−2Fe−3Al合金粉に銅粉を添加せずに、軟鋼製カプセルに封入し、熱間押出加工した。押出条件は実施例4と同じにした。押出材の組織観察、引張り試験、硬さ測定を行った。その結果を表9に示す。
Ti−15V−3Al−3Cr−3Sn合金インゴットの切削切粉を水素化し、Ti−15V−3Al−3Cr−3Sn合金の水素化物を製造、粉砕・篩別してD50=50μmの合金粉末を得た。この粉末に、実施例1で用いた電解銅粉を5%添加して、Ti−15V−3Al−3Cr−3Sn合金粉と電解銅粉からなる混合粉末を得た。この混合粉末を軟鋼製カプセルに封入し、熱間押出加工した。押出は 750℃に2時間加熱した後に実施した。押出材の組織観察、引張り試験、硬さ測定、EPMA観察を行った。結晶粒径、降伏強さ、引張り強さ、伸び、硬さを表9に示す。
実施例5で製造したTi−15V−3Al−3Cr−3Sn合金粉にCu粉を添加せずに、軟鋼製カプセルに封入し、熱間押出加工した。押出条件は実施例5と同じにした。押出材の組織観察、引張り試験、硬さ測定を行った。その結果を表9に示す。
Ti−4.5Al−3V−2Fe−2Mon合金インゴットの切削切粉を水素化し、Ti−4.5Al−3V−2Fe−2Mo合金の水素化物を製造、粉砕・篩別してD50=50μmの合金粉末を得た。この粉末に、実施例1で用いた電解銅粉を5%添加して、Ti−4.5Al−3V−2Fe−2Mo合金粉と電解銅粉からなる混合粉末を得た。この混合粉末を軟鋼製カプセルに封入し、熱間押出加工した。押出は 880℃に2時間加熱した後に実施した。押出材の組織観察、引張り試験、硬さ測定、EPMA観察を行った。結晶粒径、降伏強さ、引張り強さ、伸び、硬さを表9に示す。
実施例6で製造したTi−4.5Al−3V−2Fe−2Mo合金粉に銅粉を添加せずに、軟鋼製カプセルに封入し、熱間押出加工した。押出条件は実施例6と同じにした。押出材の組織観察、引張り試験、硬さ測定を行った。その結果を表9に示す。
Ti−5Al−5V−5Mo−3Cr合金インゴットの切削切粉を水素化し、Ti−5Al−5V−5Mo−3Cr合金の水素化物を製造、粉砕・篩別してD50=50μmの合金粉末を得た。この粉末に、実施例1で用いた電解銅粉を5%添加して、Ti−5Al−5V−5Mo−3Cr合金粉と銅粉からなる混合粉末を得た。この混合粉末を軟鋼製カプセルに封入し、熱間押出加工した。押出は840℃に2時間加熱した後に実施した。押出材の組織観察、引張り試験、硬さ測定、EPMA観察を行った。結晶粒径、降伏強さ、引張り強さ、伸び、硬さを表9に示す。
実施例7で製造したTi−5Al−5V−5Mo−3Cr合金粉に銅粉を添加せずに、軟鋼製カプセルに封入し、熱間押出加工した。押出条件は実施例7と同じにした。押出材の組織観察、引張り試験、硬さ測定を行った。その結果を表9に示す。
Ti−5Al−5V−5Mo−3Cr合金インゴットの切削切粉を水素化し、Ti−5Al−4V−0.6Mo−0.4Cr合金の水素化物を製造、粉砕・篩別してD50=50μmの合金粉末を得た。この粉末に、実施例1で用いた電解銅粉を5%添加して、Ti−5Al−4V−0.6Mo−0.4Cr合金粉と銅粉からなる混合粉末を得た。この混合粉末を軟銅製カプセルに封入し、熱間押出加工した。押出は 900℃に2時間加熱した後に実施した。押出材の組織観察、引張り試験、硬さ測定、EPMA観察を行った。結晶粒径、降伏強さ、引張り強さ、伸び、硬さを表9に示す。
実施例8で製造したTi−5Al−4V−0.6Mo−0.4Cr合金粉に銅粉を添加せずに、軟鋼製カプセルに封入し、熱間押出加工した。押出条件は実施例8と同じにした。押出材の組織観察、引張り試験、硬さ測定を行った。その結果を表9に示す。
Claims (6)
- 1~10mass%の銅を含有し、その結晶相がβ相もしくはα相およびβ相のいずれかであり、該結晶相が100μm以下の結晶粒で構成され、かつ、該結晶相の任意の部位の1mm3当たりの銅濃度が、他の任意の部位に比べて±40%以内にあることを特徴とするα+β型またはβ型チタン合金。
- 前記チタン合金が、銅粉末およびチタン合金粉末からなる混合粉を加温下において加圧成形することにより得られたものであることを特徴とする請求項1に記載のα+β型またはβ型チタン合金。
- 前記チタン合金粉末が、チタン合金を原料として製造されたものであり、該チタン合金には、アルミニウム、バナジウム、モリブデン、鉄、クロム、スズの中の少なくとも1種以上の元素が含まれていることを特徴とする請求項2に記載のα+β型またはβ型チタン合金。
- 銅を含有するα+β型チタン合金またはβ型チタン合金の製造方法であって、1~10mass%の銅粉末およびチタン合金粉末を加温下で加圧成形を施し緻密成形体とすることを特徴とするα+β型チタン合金またはβ型チタン合金の製造方法。
- 前記加温下での加圧成形温度(Tw(℃))が、(Td−100℃)<Tw<(Td+100℃)の範囲(ここで、Td(℃)は、加圧成形するチタン合金のβ変態点を表す)とすることを特徴とする請求項4に記載のα+β型チタン合金またはβ型チタン合金の製造方法。
- 前記チタン合金粉末が、チタン合金を原料として製造されたものであり、当該チタン合金には、アルミニウム、バナジウム、モリブデン、鉄、クロム、スズ、の中の少なくとも1種以上の金属元素が含まれていることを特徴とする請求項4に記載のα+β型チタン合金またはβ型チタン合金の製造方法。
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JP2018204095A (ja) * | 2017-03-29 | 2018-12-27 | ザ・ボーイング・カンパニーThe Boeing Company | チタニウム−銅−鉄合金及び関連するチクソ形成方法 |
JP2019044225A (ja) * | 2017-08-31 | 2019-03-22 | セイコーエプソン株式会社 | チタン焼結体、装飾品および時計 |
JP2023503829A (ja) * | 2019-11-15 | 2023-02-01 | ▲蘇▼州森▲鋒▼医▲療▼器械有限公司 | 高疲労強度の医療用チタン合金とその熱間加工及び熱処理方法、並びに機器 |
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